JP2017010645A - Negative electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery, and method for manufacturing negative electrode material for nonaqueous electrolyte secondary battery - Google Patents

Negative electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery, and method for manufacturing negative electrode material for nonaqueous electrolyte secondary battery Download PDF

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JP2017010645A
JP2017010645A JP2015122147A JP2015122147A JP2017010645A JP 2017010645 A JP2017010645 A JP 2017010645A JP 2015122147 A JP2015122147 A JP 2015122147A JP 2015122147 A JP2015122147 A JP 2015122147A JP 2017010645 A JP2017010645 A JP 2017010645A
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negative electrode
active material
electrode active
secondary battery
electrolyte secondary
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JP6407804B2 (en
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貴一 廣瀬
Kiichi Hirose
貴一 廣瀬
博道 加茂
Hiromichi KAMO
博道 加茂
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Shin Etsu Chemical Co Ltd
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Priority to US15/580,556 priority patent/US10418627B2/en
Priority to PCT/JP2016/002272 priority patent/WO2016203696A1/en
Priority to KR1020177036185A priority patent/KR102633418B1/en
Priority to EP16811177.1A priority patent/EP3312916B1/en
Priority to CN201680035286.4A priority patent/CN107710466B/en
Priority to TW105116332A priority patent/TWI709273B/en
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Abstract

PROBLEM TO BE SOLVED: To provide a negative electrode active material for a nonaqueous electrolyte secondary battery, high in stability against an aqueous slurry, high in capacity, and good in cycle characteristics and initial efficiency.SOLUTION: A negative electrode active material for a nonaqueous electrolyte secondary battery includes a negative electrode active material particle that contains a silicon compound (SiO: 0.5≤x≤1.6) including a Li compound. The negative electrode active material for a nonaqueous electrolyte secondary battery is characterized in that at least a part of the surface of the silicon compound is coated with a carbon film, and at least a part of the surface of the silicon compound, the surface of the carbon film, or both thereof is coated with a composite layer that includes a composite comprising an amorphous metal oxide and a metal hydroxide.SELECTED DRAWING: Figure 1

Description

本発明は、非水電解質二次電池用負極活物質及び非水電解質二次電池、並びに非水電解質二次電池用負極材の製造方法に関する。   The present invention relates to a negative electrode active material for a nonaqueous electrolyte secondary battery, a nonaqueous electrolyte secondary battery, and a method for producing a negative electrode material for a nonaqueous electrolyte secondary battery.

近年、モバイル端末などに代表される小型の電子機器が広く普及しており、さらなる小型化、軽量化及び長寿命化が強く求められている。このような市場要求に対し、特に小型かつ軽量で高エネルギー密度を得ることが可能な二次電池の開発が進められている。この二次電池は、小型の電子機器に限らず、自動車などに代表される大型の電子機器、家屋などに代表される電力貯蔵システムへの適用も検討されている。   In recent years, small electronic devices typified by mobile terminals have been widely used, and further downsizing, weight reduction, and long life have been strongly demanded. In response to such market demands, development of secondary batteries capable of obtaining a high energy density, in particular, being small and light is underway. This secondary battery is not limited to a small electronic device, but is also considered to be applied to a large-sized electronic device represented by an automobile or the like, or an electric power storage system represented by a house.

その中でも、リチウムイオン二次電池は小型かつ高容量化が行いやすく、また、鉛電池、ニッケルカドミウム電池よりも高いエネルギー密度が得られるため、大いに期待されている。   Among them, lithium ion secondary batteries are highly expected because they are small and easy to increase in capacity, and can obtain higher energy density than lead batteries and nickel cadmium batteries.

上記のリチウムイオン二次電池は、正極および負極、セパレータと共に電解液を備えており、負極は充放電反応に関わる負極活物質を含んでいる。   Said lithium ion secondary battery is equipped with the electrolyte solution with the positive electrode, the negative electrode, and the separator, and the negative electrode contains the negative electrode active material in connection with charging / discharging reaction.

この負極活物質としては、炭素材料が広く使用されている一方で、最近の市場要求から電池容量のさらなる向上が求められている。電池容量向上のために、負極活物質材としてケイ素を用いることが検討されている。なぜならば、ケイ素の理論容量（４１９９ｍＡｈ／ｇ）は黒鉛の理論容量（３７２ｍＡｈ／ｇ）よりも１０倍以上大きいため、電池容量の大幅な向上を期待できるからである。負極活物質材としてのケイ素材の開発はケイ素単体だけではなく、合金、酸化物に代表される化合物などについても検討されている。また、活物質形状は、炭素材では標準的な塗布型から、集電体に直接堆積する一体型まで検討されている。   As this negative electrode active material, a carbon material is widely used, but further improvement in battery capacity is required due to recent market demand. In order to improve battery capacity, use of silicon as a negative electrode active material has been studied. This is because the theoretical capacity of silicon (4199 mAh / g) is 10 times or more larger than the theoretical capacity of graphite (372 mAh / g), so that significant improvement in battery capacity can be expected. The development of a siliceous material as a negative electrode active material has been examined not only for silicon itself but also for compounds represented by alloys and oxides. In addition, the shape of the active material has been studied from a standard coating type for carbon materials to an integrated type directly deposited on a current collector.

しかしながら、負極活物質としてケイ素を主原料として用いると、充放電時に負極活物質が膨張及び収縮するため、主に負極活物質表層近傍で割れやすくなる。また、活物質内部にイオン性物質が生成し、負極活物質が割れやすい物質となる。負極活物質表層が割れると、それによって新表面が生じ、活物質の反応面積が増加する。この時、新表面において電解液の分解反応が生じるとともに、新表面に電解液の分解物である被膜が形成されるため電解液が消費される。このためサイクル特性が低下しやすくなる。   However, when silicon is used as the negative electrode active material as the main raw material, the negative electrode active material expands and contracts during charge and discharge, and therefore, it tends to break mainly near the surface of the negative electrode active material. Further, an ionic material is generated inside the active material, and the negative electrode active material is easily broken. When the negative electrode active material surface layer is cracked, a new surface is generated thereby increasing the reaction area of the active material. At this time, a decomposition reaction of the electrolytic solution occurs on the new surface, and a coating that is a decomposition product of the electrolytic solution is formed on the new surface. For this reason, the cycle characteristics are likely to deteriorate.

これまでに、電池初期効率やサイクル特性を向上させるために、ケイ素材を主材としたリチウムイオン二次電池用負極材料、電極構成についてさまざまな検討がなされている。   To date, various studies have been made on negative electrode materials and electrode configurations for lithium ion secondary batteries mainly composed of a siliceous material in order to improve battery initial efficiency and cycle characteristics.

具体的には、良好なサイクル特性や高い安全性を得る目的で、気相法を用いケイ素及びアモルファス二酸化ケイ素を同時に堆積させている（例えば特許文献１参照）。また、高い電池容量や安全性を得るために、ケイ素酸化物粒子の表層に炭素材（電子伝導材）を設けている（例えば特許文献２参照）。さらに、サイクル特性を改善するとともに高入出力特性を得るために、ケイ素及び酸素を含有する活物質を作製し、かつ、集電体近傍での酸素比率が高い活物質層を形成している（例えば特許文献３参照）。また、サイクル特性を向上させるために、ケイ素活物質中に酸素を含有させ、平均酸素含有量が４０ａｔ％以下であり、かつ集電体に近い場所で酸素含有量が多くなるように形成している（例えば特許文献４参照）。   Specifically, for the purpose of obtaining good cycle characteristics and high safety, silicon and amorphous silicon dioxide are deposited simultaneously using a vapor phase method (see, for example, Patent Document 1). Further, in order to obtain a high battery capacity and safety, a carbon material (electron conductive material) is provided on the surface layer of the silicon oxide particles (see, for example, Patent Document 2). Furthermore, in order to improve cycle characteristics and obtain high input / output characteristics, an active material containing silicon and oxygen is produced, and an active material layer having a high oxygen ratio in the vicinity of the current collector is formed ( For example, see Patent Document 3). Further, in order to improve the cycle characteristics, oxygen is contained in the silicon active material, the average oxygen content is 40 at% or less, and the oxygen content is increased at a location close to the current collector. (For example, refer to Patent Document 4).

また、初回充放電効率を改善するためにＳｉ相、ＳｉＯ２、ＭｙＯ金属酸化物を含有するナノ複合体を用いている（例えば特許文献５参照）。また、サイクル特性改善のため、ＳｉＯｘ（０．８≦ｘ≦１．５、粒径範囲＝１μｍ〜５０μｍ）と炭素材を混合して高温焼成している（例えば特許文献６参照）。また、サイクル特性改善のために、負極活物質中におけるケイ素に対する酸素のモル比を０．１〜１．２とし、活物質、集電体界面近傍におけるモル比の最大値、最小値との差が０．４以下となる範囲で活物質の制御を行っている（例えば特許文献７参照）。また、電池負荷特性を向上させるため、リチウムを含有した金属酸化物を用いている（例えば特許文献８参照）。また、サイクル特性を改善させるために、ケイ素材表層にシラン化合物などの疎水層を形成している（例えば特許文献９参照）。 Further, Si phase, (for example, see Patent Document 5) by using a nanocomposite containing SiO 2, M y O metal oxide in order to improve the initial charge and discharge efficiency. In order to improve cycle characteristics, SiO x (0.8 ≦ x ≦ 1.5, particle size range = 1 μm to 50 μm) and a carbon material are mixed and fired at a high temperature (see, for example, Patent Document 6). Further, in order to improve cycle characteristics, the molar ratio of oxygen to silicon in the negative electrode active material is set to 0.1 to 1.2, and the difference between the maximum value and the minimum value of the molar ratio in the vicinity of the active material and current collector interface The active material is controlled within a range of 0.4 or less (see, for example, Patent Document 7). Further, in order to improve battery load characteristics, a metal oxide containing lithium is used (see, for example, Patent Document 8). Further, in order to improve cycle characteristics, a hydrophobic layer such as a silane compound is formed on the surface layer of the siliceous material (see, for example, Patent Document 9).

また、サイクル特性改善のため、酸化ケイ素を用い、その表層に黒鉛被膜を形成することで導電性を付与している（例えば特許文献１０参照）。特許文献１０において、黒鉛被膜に関するラマンスペクトルから得られるシフト値に関して、１３３０ｃｍ−１及び１５８０ｃｍ−１にブロードなピークが現れるとともに、それらの強度比Ｉ１３３０／Ｉ１５８０が１．５＜Ｉ１３３０／Ｉ１５８０＜３となっている。また、高い電池容量、サイクル特性の改善のため、二酸化ケイ素中に分散されたケイ素微結晶相を有する粒子を用いている（例えば、特許文献１１参照）。また、過充電、過放電特性を向上させるために、ケイ素と酸素の原子数比を１：ｙ（０＜ｙ＜２）に制御したケイ素酸化物を用いている（例えば特許文献１２参照）。また、高い電池容量、サイクル特性の改善のため、ケイ素と炭素の混合電極を作成しケイ素比率を５ｗｔ％以上１３ｗｔ％以下で設計している（例えば、特許文献１３参照）。 Further, in order to improve cycle characteristics, conductivity is imparted by using silicon oxide and forming a graphite film on the surface layer (see, for example, Patent Document 10). In Patent Document 10, with respect to the shift value obtained from the Raman spectra for graphite coating, with broad peaks appearing at 1330 cm -1 and 1580 cm -1, their intensity ratio I 1330 / I 1580 is 1.5 <I 1330 / I 1580 <3. In addition, particles having a silicon microcrystalline phase dispersed in silicon dioxide are used in order to improve high battery capacity and cycle characteristics (see, for example, Patent Document 11). Further, in order to improve overcharge and overdischarge characteristics, silicon oxide in which the atomic ratio of silicon and oxygen is controlled to 1: y (0 <y <2) is used (see, for example, Patent Document 12). In addition, in order to improve high battery capacity and cycle characteristics, a mixed electrode of silicon and carbon is prepared and the silicon ratio is designed to be 5 wt% or more and 13 wt% or less (see, for example, Patent Document 13).

特開２００１−１８５１２７号公報JP 2001-185127 A 特開２００２−０４２８０６号公報JP 2002-042806 A 特開２００６−１６４９５４号公報JP 2006-164955 A 特開２００６−１１４４５４号公報JP 2006-114454 A 特開２００９−０７０８２５号公報JP 2009-070825 A 特開２００８−２８２８１９号公報JP 2008-282819 A 特開２００８−２５１３６９号公報JP 2008-251369 A 特開２００８−１７７３４６号公報JP 2008-177346 A 特開２００７−２３４２５５号公報JP 2007-234255 A 特開２００９−２１２０７４号公報JP 2009-212074 A 特開２００９−２０５９５０号公報JP 2009-205950 A 特許第２９９７７４１号明細書Japanese Patent No. 2,997,741 特開２０１０−０９２８３０号公報JP 2010-092830 A

上述したように、近年、モバイル端末などに代表される小型の電子機器は高性能化、多機能化がすすめられており、その主電源であるリチウムイオン二次電池は電池容量の増加が求められている。この問題を解決する１つの手法として、ケイ素材を主材として用いた負極からなるリチウムイオン二次電池の開発が望まれている。   As described above, in recent years, small electronic devices typified by mobile terminals and the like have been improved in performance and multifunction, and the lithium ion secondary battery as the main power source is required to increase the battery capacity. ing. As one method for solving this problem, development of a lithium ion secondary battery composed of a negative electrode using a siliceous material as a main material is desired.

また、ケイ素材を用いたリチウムイオン二次電池は、炭素材を用いたリチウムイオン二次電池と同等に近い電池特性が望まれている。そこで、Ｌｉの挿入、一部脱離により改質されたケイ素酸化物を負極活物質として使用することで、電池のサイクル維持率、及び初回効率を改善してきた。しかしながら、改質後のケイ素酸化物はＬｉを用いて改質されたため、比較的耐水性が低い。そのため、負極の製造時に作製する、上記改質後のケイ素酸化物を含むスラリーの安定化が不十分となりスラリーの経時変化によってガスが発生することがあり、炭素系活物質の塗布に従来から一般的に使われている装置等を使用することができない場合が有ったり、または使用しづらいという問題があった。このように、Ｌｉを用いた改質によって、初期効率及びサイクル維持率を改善したケイ素酸化物を使用する場合、水を含むスラリーの安定性が不十分となるため、二次電池の工業的な生産において優位な非水電解質二次電池用負極活物質を提案するには至っていなかった。   Moreover, the lithium ion secondary battery using a siliceous material is desired to have a battery characteristic close to that of a lithium ion secondary battery using a carbon material. Thus, the use of silicon oxide modified by insertion and partial desorption of Li as the negative electrode active material has improved the cycle retention rate and initial efficiency of the battery. However, since the modified silicon oxide has been modified using Li, its water resistance is relatively low. For this reason, the slurry containing the modified silicon oxide prepared during the production of the negative electrode is not sufficiently stabilized, and gas may be generated due to aging of the slurry. In some cases, it is difficult to use a device or the like that is used in general, or it is difficult to use. As described above, when using silicon oxide whose initial efficiency and cycle retention ratio are improved by modification with Li, the stability of the slurry containing water becomes insufficient. A negative electrode active material for a non-aqueous electrolyte secondary battery superior in production has not been proposed.

本発明は前述のような問題に鑑みてなされたもので、水系スラリーに対する安定性が高く、高容量であるとともに、サイクル特性及び初回効率が良好な非水電解質二次電池用負極活物質を提供することを目的とする。   The present invention has been made in view of the above problems, and provides a negative electrode active material for a non-aqueous electrolyte secondary battery that has high stability with respect to an aqueous slurry, high capacity, and good cycle characteristics and initial efficiency. The purpose is to do.

上記目的を達成するために、本発明は、負極活物質粒子を有し、該負極活物質粒子はＬｉ化合物が含まれるケイ素化合物（ＳｉＯｘ：０．５≦ｘ≦１．６）を含有するものである非水電解質二次電池用負極活物質であって、前記ケイ素化合物の表面の少なくとも一部が炭素被膜で被覆されたものであり、前記ケイ素化合物の表面若しくは前記炭素被膜の表面、又はこれらの両方の少なくとも一部が、非晶質の金属酸化物及び金属水酸化物から成る複合体を含む複合層で被覆されたものであることを特徴とする非水電解質二次電池用負極活物質を提供する。 In order to achieve the above object, the present invention has negative electrode active material particles, and the negative electrode active material particles contain a silicon compound containing a Li compound (SiO x : 0.5 ≦ x ≦ 1.6). A negative electrode active material for a non-aqueous electrolyte secondary battery, wherein at least part of the surface of the silicon compound is coated with a carbon coating, or the surface of the silicon compound or the surface of the carbon coating, or A negative electrode active for a non-aqueous electrolyte secondary battery, wherein at least a part of both of them is coated with a composite layer containing a composite made of an amorphous metal oxide and a metal hydroxide. Provide material.

本発明の負極活物質は、ケイ素化合物を含有する負極活物質粒子（以下、ケイ素系活物質粒子とも呼称する）が、その最表面に、非晶質の金属酸化物及び金属水酸化物から成る複合体を含む複合層を有しているため、水系スラリーに対しての耐水性が高いものとなる。また、上記複合体が非晶質であれば、Ｌｉの授受が行われやすい。また、本発明は、ケイ素化合物の表面の少なくとも一部が炭素被膜で被覆されたものであるため、導電性に優れる。そのため、本発明の負極活物質を使用すれば、Ｌｉを用いて改質されたケイ素酸化物本来の特性を生かした高い電池容量及び良好なサイクル維持率を有する非水電解質二次電池を工業的な生産において優位に製造可能となる。   In the negative electrode active material of the present invention, negative electrode active material particles containing a silicon compound (hereinafter also referred to as silicon-based active material particles) are composed of amorphous metal oxide and metal hydroxide on the outermost surface. Since the composite layer containing the composite is included, the water resistance against the aqueous slurry is high. Further, when the composite is amorphous, Li is easily exchanged. Further, the present invention is excellent in conductivity because at least a part of the surface of the silicon compound is coated with a carbon film. Therefore, if the negative electrode active material of the present invention is used, a non-aqueous electrolyte secondary battery having a high battery capacity and a good cycle maintenance ratio utilizing the original characteristics of silicon oxide modified with Li can be industrially produced. Manufacturing in an advantageous production.

このとき、前記金属酸化物及び金属水酸化物は、アルミニウム、マグネシウム、チタニウム、及びジルコニウムのうち少なくとも１種の元素を含むことが好ましい。   At this time, it is preferable that the metal oxide and the metal hydroxide contain at least one element of aluminum, magnesium, titanium, and zirconium.

金属酸化物及び金属水酸化物が上記のような金属元素を含むことで、電極作製時にスラリーがより安定する。   When the metal oxide and the metal hydroxide contain the metal element as described above, the slurry becomes more stable when the electrode is manufactured.

またこのとき、前記複合層の厚さが１０ｎｍ以下であることが好ましい。また、前記複合層の厚さが５ｎｍ以下であることが特に好ましい。   At this time, the thickness of the composite layer is preferably 10 nm or less. Moreover, it is particularly preferable that the thickness of the composite layer is 5 nm or less.

複合層の厚さが１０ｎｍ以下、特には５ｎｍ以下であれば、ケイ素系活物質粒子の抵抗が大きくなり過ぎないため、良好な電池特性が得られる。   If the thickness of the composite layer is 10 nm or less, particularly 5 nm or less, the resistance of the silicon-based active material particles does not become excessively high, and good battery characteristics can be obtained.

このとき、前記ケイ素化合物は、前記Ｌｉ化合物としてＬｉ２ＳｉＯ３を含むことが好ましい。 At this time, the silicon compound preferably contains Li 2 SiO 3 as the Li compound.

Ｌｉ２ＳｉＯ３のようなＬｉシリケートは、Ｌｉ化合物として比較的安定しているため、より良好な電池特性が得られる。 Since Li silicate such as Li 2 SiO 3 is relatively stable as a Li compound, better battery characteristics can be obtained.

またこのとき、前記ケイ素化合物が、２９Ｓｉ−ＭＡＳ−ＮＭＲ スペクトルから得られるケミカルシフト値として−９５〜−１５０ｐｐｍに与えられるＳｉＯ２領域に由来するピークを持つことが好ましい。 Moreover, at this time, it is preferable that the silicon compound has a peak derived from a SiO 2 region given to -95 to -150 ppm as a chemical shift value obtained from a 29 Si-MAS-NMR spectrum.

このようなものであれば、ケイ素化合物中のＬｉシリケート等のＬｉ化合物の量が過多となっておらず、ＳｉＯ２成分がある程度残っているため、電極作製時のスラリーに対する安定性がより向上する。 In such a case, the amount of Li compound such as Li silicate in the silicon compound is not excessive, and the SiO 2 component remains to some extent, so that the stability to the slurry during electrode preparation is further improved. .

このとき、前記ケイ素化合物が、２９Ｓｉ−ＭＡＳ−ＮＭＲ スペクトルから得られるケミカルシフト値として−７５ｐｐｍ付近に与えられるＬｉ２ＳｉＯ３に由来するピークの強度Ａと、−９５〜−１５０ｐｐｍに与えられるＳｉＯ２領域に由来するピークの強度Ｂとが、Ａ＞Ｂの関係を満たすことが好ましい。 At this time, the silicon compound has a peak intensity A derived from Li 2 SiO 3 given in the vicinity of −75 ppm as a chemical shift value obtained from the 29 Si-MAS-NMR spectrum, and SiO given to −95 to −150 ppm. The intensity B of the peak derived from the two regions preferably satisfies the relationship A> B.

このように、ケイ素化合物中において、ＳｉＯ２成分を基準としてＬｉ２ＳｉＯ３の量がより多いものであれば、Ｌｉの挿入による電池特性の向上効果を十分に得られる負極活物質となる。 Thus, in the silicon compound, if the amount of Li 2 SiO 3 is larger with respect to the SiO 2 component, it becomes a negative electrode active material that can sufficiently obtain the effect of improving battery characteristics by inserting Li.

またこのとき、前記非水電解質二次電池用負極活物質と炭素系活物質とを混合した負極活物質を使用して作製した負極電極と対極リチウムとから成る試験セルを充放電し、放電容量Ｑを前記対極リチウムを基準とする前記負極電極の電位Ｖで微分した微分値ｄＱ／ｄＶと前記電位Ｖとの関係を示すグラフを描いた場合に、前記非水電解質二次電池用負極活物質がリチウムを脱離するよう電流を流す放電時における、前記負極電極の電位Ｖが０．４０Ｖ〜０．５５Ｖの範囲にピークを有するものであることが好ましい。   At this time, a test cell comprising a negative electrode and a counter electrode lithium prepared by using a negative electrode active material obtained by mixing the negative electrode active material for a nonaqueous electrolyte secondary battery and a carbon-based active material is charged and discharged, and a discharge capacity is obtained. When a graph showing the relationship between the differential value dQ / dV obtained by differentiating Q from the potential V of the negative electrode with respect to the counter lithium and the potential V is drawn, the negative electrode active material for a non-aqueous electrolyte secondary battery It is preferable that the electric potential V of the negative electrode has a peak in the range of 0.40 V to 0.55 V at the time of discharging in which a current is applied so as to desorb lithium.

Ｖ−ｄＱ／ｄＶ曲線における上記のピークはケイ素材のピークと類似しており、より高電位側における放電カーブが鋭く立ち上がるため、電池設計を行う際、容量発現しやすくなる。   The above peak in the V-dQ / dV curve is similar to the peak of the siliceous material, and the discharge curve on the higher potential side rises sharply, so that the capacity is easily developed when designing the battery.

このとき、前記ケイ素化合物が、Ｘ線回折により得られるＳｉ（１１１）結晶面に起因する回折ピークの半値幅（２θ）が１．２°以上であると共に、その結晶面に起因する結晶子サイズが７．５ｎｍ以下のものであることが好ましい。   At this time, the half width (2θ) of the diffraction peak attributed to the Si (111) crystal plane obtained by X-ray diffraction of the silicon compound is 1.2 ° or more, and the crystallite size attributed to the crystal plane Is preferably 7.5 nm or less.

このような半値幅及び結晶子サイズを有するケイ素系活物質は、結晶性が低くＳｉ結晶の存在量が少ないため、電池特性を向上させることができる。   Since the silicon-based active material having such a half-value width and crystallite size has low crystallinity and a small amount of Si crystals, battery characteristics can be improved.

またこのとき、前記ケイ素化合物のメディアン径が０．５μｍ以上１５μｍ以下のものであることが好ましい。   At this time, the median diameter of the silicon compound is preferably 0.5 μm or more and 15 μm or less.

メディアン径が０．５μｍ以上であれば、ケイ素化合物の表面における副反応が起きる面積が小さいため、Ｌｉを余分に消費せず、電池のサイクル維持率を高く維持できる。また、メディアン径が１５μｍ以下であれば、Ｌｉ挿入時の膨張が小さく、割れ難くなり、かつ、亀裂が生じにくい。さらに、ケイ素化合物の膨張が小さいため、例えば一般的に使用されているケイ素系活物質に炭素活物質を混合した負極活物質層などが破壊され難い。   When the median diameter is 0.5 μm or more, the area where the side reaction occurs on the surface of the silicon compound is small, so that Li is not consumed excessively and the cycle maintenance rate of the battery can be maintained high. Further, if the median diameter is 15 μm or less, the expansion at the time of inserting Li is small, it is difficult to crack, and cracks are hardly generated. Furthermore, since the expansion of the silicon compound is small, for example, a negative electrode active material layer in which a carbon active material is mixed with a commonly used silicon-based active material is not easily destroyed.

また、上記目的を達成するために、本発明は、上記のいずれかの非水電解質二次電池用負極活物質を含むことを特徴とする非水電解質二次電池を提供する。   Moreover, in order to achieve the said objective, this invention provides the nonaqueous electrolyte secondary battery characterized by including any one of said negative electrode active materials for nonaqueous electrolyte secondary batteries.

このような二次電池は、高いサイクル維持率及び初回効率を有するとともに、工業的に優位に製造することが可能なものである。   Such a secondary battery has a high cycle maintenance ratio and initial efficiency, and can be manufactured industrially.

また、上記目的を達成するために、本発明は、負極活物質粒子を含む非水電解質二次電池用負極材の製造方法であって、一般式ＳｉＯｘ（０．５≦ｘ≦１．６）で表される酸化珪素粒子を作製する工程と、前記酸化珪素粒子の表面に炭素被膜を形成する工程と、前記炭素被膜が被覆された酸化珪素粒子に、Ｌｉを挿入、脱離することで、前記酸化珪素粒子を改質する工程と、前記改質後の酸化珪素粒子の表面に、非晶質の金属酸化物及び金属水酸化物から成る複合体を含む複合層を形成する工程とを有し、前記複合層を形成された酸化珪素粒子を用いて、非水電解質二次電池用負極材を製造することを特徴とする非水電解質二次電池用負極材の製造方法を提供する。 In order to achieve the above object, the present invention provides a method for producing a negative electrode material for a non-aqueous electrolyte secondary battery including negative electrode active material particles, which has a general formula SiO x (0.5 ≦ x ≦ 1.6). ), A step of forming a carbon film on the surface of the silicon oxide particles, and insertion and desorption of Li from the silicon oxide particles coated with the carbon film. A step of modifying the silicon oxide particles, and a step of forming a composite layer including a composite of an amorphous metal oxide and a metal hydroxide on the surface of the modified silicon oxide particles. A negative electrode material for a non-aqueous electrolyte secondary battery is manufactured using the silicon oxide particles having the composite layer and having the composite layer formed therein.

このような非水電解質二次電池用負極材の製造方法であれば、Ｌｉを用いて改質されたケイ素酸化物本来の特性を生かした高い電池容量及び良好なサイクル維持率を有する非水負極材を得ることができる。さらにこのようにして製造された負極材は、上記のような複合層を有するケイ素系活物質粒子を含有しているため、負極の製造時に作製するスラリーが安定なものとなる。すなわち、二次電池を工業的に優位に生産可能な負極材を得ることができる。   If it is a manufacturing method of such a negative electrode material for nonaqueous electrolyte secondary batteries, the nonaqueous negative electrode which has the high battery capacity and the favorable cycle maintenance factor which utilized the original characteristic of the silicon oxide modified using Li A material can be obtained. Furthermore, since the negative electrode material manufactured in this way contains the silicon-based active material particles having the composite layer as described above, the slurry produced at the time of manufacturing the negative electrode becomes stable. That is, a negative electrode material capable of industrially producing a secondary battery can be obtained.

このとき、前記複合層形成工程において、金属アルコキシドの加水分解及び脱水縮合によって前記改質後の酸化珪素粒子の表面に前記複合層を形成することが好ましい。   At this time, in the composite layer forming step, it is preferable that the composite layer is formed on the surface of the modified silicon oxide particles by hydrolysis and dehydration condensation of a metal alkoxide.

このようにすれば、金属アルコキシドの加水分解・脱水縮合が連続して起こることで、金属酸化物領域と金属水酸化物領域が両立するように複合体を効率よく生成することができる。   If it does in this way, a hydrolysis and dehydration condensation of a metal alkoxide will occur continuously, and a complex can be efficiently generated so that a metal oxide field and a metal hydroxide field may be compatible.

本発明の負極活物質は、二次電池の製造時に作製するスラリーの安定性を向上させることができ、このスラリーを用いれば、工業的に使用可能な塗膜を形成できるので、実質的に電池容量、サイクル特性、及び初回充放電特性を向上させることができる。また、この負極活物質を含む本発明の二次電池は、工業的に優位に生産可能であり、電池容量、サイクル特性、及び初回充放電特性が良好なものとなる。また、本発明の二次電池を用いた電子機器、電動工具、電気自動車及び電力貯蔵システム等でも同様の効果を得ることができる。   The negative electrode active material of the present invention can improve the stability of the slurry produced during the production of the secondary battery, and if this slurry is used, an industrially usable coating film can be formed. Capacity, cycle characteristics, and initial charge / discharge characteristics can be improved. Moreover, the secondary battery of the present invention containing this negative electrode active material can be produced industrially superiorly, and the battery capacity, cycle characteristics, and initial charge / discharge characteristics are good. Moreover, the same effect can be acquired also in the electronic device, electric tool, electric vehicle, electric power storage system, etc. which used the secondary battery of this invention.

また、本発明の負極材の製造方法は、二次電池の製造時に作製するスラリーの安定性を向上させ、かつ、電池容量、サイクル特性、及び初回充放電特性を向上させることができる負極材を製造できる。   Further, the method for producing a negative electrode material of the present invention provides a negative electrode material that can improve the stability of a slurry produced during the production of a secondary battery and can improve battery capacity, cycle characteristics, and initial charge / discharge characteristics. Can be manufactured.

本発明の負極活物質に含まれるケイ素系活物質粒子の複合層付近の構成の概略を示す図である。It is a figure which shows the outline of a structure of the composite layer vicinity of the silicon type active material particle contained in the negative electrode active material of this invention. 本発明の負極活物質を含む負極の構成を示す断面図である。It is sectional drawing which shows the structure of the negative electrode containing the negative electrode active material of this invention. 本発明の負極活物質を製造する際に使用できるバルク内改質装置である。It is an in-bulk reformer that can be used when producing the negative electrode active material of the present invention. 本発明の負極活物質を含むリチウムイオン二次電池の構成例（ラミネートフィルム型）を表す分解図である。It is an exploded view showing the structural example (laminate film type) of the lithium ion secondary battery containing the negative electrode active material of this invention. 実施例１−１においてケイ素化合物から測定された２９Ｓｉ−ＭＡＳ−ＮＭＲスペクトルである．It is a 29 Si-MAS-NMR spectrum measured from the silicon compound in Example 1-1.

以下、本発明について実施の形態を説明するが、本発明はこれに限定されるものではない。   Hereinafter, although an embodiment is described about the present invention, the present invention is not limited to this.

前述のように、リチウムイオン二次電池の電池容量を増加させる１つの手法として、ケイ素系活物質を主材として用いた負極をリチウムイオン二次電池の負極として用いることが検討されている。ケイ素系活物質を主材として用いたリチウムイオン二次電池は、炭素材を用いたリチウムイオン二次電池と同等に近いサイクル特性、初期効率が望まれているが、炭素材を用いたリチウムイオン二次電池と同等に近いサイクル特性、初期効率を得るためにＬｉを用いて改質したケイ素系活物質では安定したスラリーの作製が難しく、良質な負極電極を製造することは困難であった。   As described above, as one method for increasing the battery capacity of a lithium ion secondary battery, the use of a negative electrode using a silicon-based active material as a main material as a negative electrode of a lithium ion secondary battery has been studied. Lithium ion secondary batteries using silicon-based active materials as the main material are expected to have cycle characteristics and initial efficiency close to those of lithium ion secondary batteries using carbon materials. With a silicon-based active material modified with Li in order to obtain cycle characteristics and initial efficiency close to those of a secondary battery, it is difficult to produce a stable slurry, and it is difficult to produce a good quality negative electrode.

そこで、本発明者らは、高電池容量であるとともに、サイクル特性及び初回効率が良好な非水電解質二次電池を容易に製造することが可能な負極活物質を得るために鋭意検討を重ね、本発明に至った。   Therefore, the present inventors have made extensive studies in order to obtain a negative electrode active material capable of easily producing a nonaqueous electrolyte secondary battery having a high battery capacity and good cycle characteristics and initial efficiency. The present invention has been reached.

本発明の負極活物質は、Ｌｉ化合物が含まれるケイ素化合物（ＳｉＯｘ：０．５≦ｘ≦１．６）を有するケイ素系活物質粒子を含む。また、この負極活物質は、ケイ素化合物の表面の少なくとも一部に炭素被膜が形成されている。さらに、この負極活物質は、ケイ素化合物の表面若しくは炭素被膜の表面、又はこれらの両方の少なくとも一部が、非晶質の金属酸化物及び金属水酸化物から成る複合体を含む複合層で被覆されている。 The negative electrode active material of the present invention includes silicon-based active material particles having a silicon compound (SiO x : 0.5 ≦ x ≦ 1.6) containing a Li compound. The negative electrode active material has a carbon film formed on at least a part of the surface of the silicon compound. Furthermore, the negative electrode active material is coated with a composite layer including a composite composed of an amorphous metal oxide and a metal hydroxide, at least a part of the surface of the silicon compound or the surface of the carbon film, or both of them. Has been.

ここで、図１に、ケイ素化合物１の表層部付近の概略を示す。図１のように、ケイ素化合物１の表面には炭素被膜２が形成されている。図１の場合、ケイ素化合物の表面の一部に炭素被膜が形成されているが、炭素被膜はケイ素化合物の全面に形成されていても良い。また、ケイ素化合物１の表面と炭素被膜２の表面には、非晶質のアルミニウム酸化物及びアルミニウム水酸化物から成る複合体を含む複合層３が形成されている。図１では、複合層３の複合体がアルミニウム元素を含む場合を例示しているが、これに特に限定されることは無く、他の金属元素を含んでいても良い。この場合、複合層３は、図１に示すように、アルミニウム酸化物領域３ａとアルミニウム水酸化物領域３ｂを有する。   Here, FIG. 1 shows an outline of the vicinity of the surface layer portion of the silicon compound 1. As shown in FIG. 1, a carbon film 2 is formed on the surface of the silicon compound 1. In the case of FIG. 1, the carbon film is formed on a part of the surface of the silicon compound. However, the carbon film may be formed on the entire surface of the silicon compound. A composite layer 3 including a composite made of amorphous aluminum oxide and aluminum hydroxide is formed on the surface of the silicon compound 1 and the surface of the carbon coating 2. Although FIG. 1 illustrates the case where the composite of the composite layer 3 contains an aluminum element, it is not particularly limited to this and may contain other metal elements. In this case, the composite layer 3 has an aluminum oxide region 3a and an aluminum hydroxide region 3b as shown in FIG.

このような負極活物質は、ケイ素系活物質粒子が、その最表面に、非晶質の金属酸化物及び金属水酸化物から成る複合体を含む複合層を有しているため、水系スラリーに対しての耐水性が高いものとなる。従来、Ｌｉの挿入、脱離によって改質したケイ素酸化物を含む水系スラリーは経時変化して、ガス発生が起こるため、量産化に不向きであった。しかしながら、本発明では、ケイ素系活物質粒子が、上記のような複合層を有することで、スラリーの経時変化に伴うガス発生が起こりづらくなり、安定した塗膜を得ることができ、結着性を十分に確保することができる。また、上記複合体が非晶質であれば、Ｌｉの授受が行われやすい。また、本発明は、ケイ素化合物の表面の少なくとも一部が炭素被膜で被覆されたものであるため、導電性に優れる。そのため、本発明の負極活物質を使用すれば、Ｌｉを用いて改質されたケイ素酸化物本来の特性を生かした高い電池容量及び良好なサイクル維持率を有する非水電解質二次電池を工業的な生産において優位に製造可能となる。   In such a negative electrode active material, since the silicon-based active material particles have a composite layer containing a composite composed of an amorphous metal oxide and a metal hydroxide on the outermost surface, In contrast, the water resistance is high. Conventionally, an aqueous slurry containing a silicon oxide modified by insertion and desorption of Li changes with time and gas is generated, which is not suitable for mass production. However, in the present invention, since the silicon-based active material particles have the composite layer as described above, it is difficult for gas generation due to aging of the slurry to occur, and a stable coating film can be obtained. Can be secured sufficiently. Further, when the composite is amorphous, Li is easily exchanged. Further, the present invention is excellent in conductivity because at least a part of the surface of the silicon compound is coated with a carbon film. Therefore, if the negative electrode active material of the present invention is used, a non-aqueous electrolyte secondary battery having a high battery capacity and a good cycle maintenance ratio utilizing the original characteristics of silicon oxide modified with Li can be industrially produced. Manufacturing in an advantageous production.

［負極の構成］
続いて、このような本発明の負極活物質を含む二次電池の負極の構成について説明する。 [Configuration of negative electrode]
Then, the structure of the negative electrode of the secondary battery containing such a negative electrode active material of this invention is demonstrated.

図２は、本発明の負極活物質を含む負極の断面図を表している。図２に示すように、負極１０は、負極集電体１１の上に負極活物質層１２を有する構成になっている。この負極活物質層１２は負極集電体１１の両面、又は、片面だけに設けられていても良い。さらに、本発明の非水電解質二次電池の負極においては、負極集電体１１はなくてもよい。   FIG. 2 shows a cross-sectional view of a negative electrode containing the negative electrode active material of the present invention. As shown in FIG. 2, the negative electrode 10 is configured to have a negative electrode active material layer 12 on a negative electrode current collector 11. The negative electrode active material layer 12 may be provided on both surfaces or only one surface of the negative electrode current collector 11. Furthermore, the negative electrode current collector 11 may not be provided in the negative electrode of the nonaqueous electrolyte secondary battery of the present invention.

［負極集電体］
負極集電体１１は、優れた導電性材料であり、かつ、機械的な強度に長けた物で構成される。負極集電体１１に用いることができる導電性材料として、例えば銅（Ｃｕ）やニッケル（Ｎｉ）があげられる。この導電性材料は、リチウム（Ｌｉ）と金属間化合物を形成しない材料であることが好ましい。 [Negative electrode current collector]
The negative electrode current collector 11 is an excellent conductive material and is made of a material that is excellent in mechanical strength. Examples of the conductive material that can be used for the negative electrode current collector 11 include copper (Cu) and nickel (Ni). This conductive material is preferably a material that does not form an intermetallic compound with lithium (Li).

負極集電体１１は、主元素以外に炭素（Ｃ）や硫黄（Ｓ）を含んでいることが好ましい。負極集電体の物理的強度が向上するためである。特に、充電時に膨張する活物質層を有する場合、集電体が上記の元素を含んでいれば、集電体を含む電極変形を抑制する効果があるからである。上記の含有元素の含有量は、特に限定されないが、中でも、１００ｐｐｍ以下であることが好ましい。これは、より高い変形抑制効果が得られるからである。   The negative electrode current collector 11 preferably contains carbon (C) or sulfur (S) in addition to the main element. This is because the physical strength of the negative electrode current collector is improved. In particular, in the case of having an active material layer that expands during charging, if the current collector contains the above-described element, there is an effect of suppressing electrode deformation including the current collector. Although content of said content element is not specifically limited, Especially, it is preferable that it is 100 ppm or less. This is because a higher deformation suppressing effect can be obtained.

負極集電体１１の表面は、粗化されていても良いし、粗化されていなくても良い。粗化されている負極集電体は、例えば、電解処理、エンボス処理、又は化学エッチングされた金属箔などである。粗化されていない負極集電体は例えば、圧延金属箔などである。   The surface of the negative electrode current collector 11 may be roughened or may not be roughened. The roughened negative electrode current collector is, for example, a metal foil subjected to electrolytic treatment, embossing treatment, or chemical etching. The non-roughened negative electrode current collector is, for example, a rolled metal foil.

［負極活物質層］
負極活物質層１２は、ケイ素系活物質粒子の他に炭素系活物質などの複数の種類の負極活物質を含んでいて良い。さらに、電池設計上、増粘剤（「結着剤」、「バインダー」とも呼称する）や導電助剤等の他の材料を含んでいても良い。また、負極活物質の形状は粒子状であって良い。 [Negative electrode active material layer]
The negative electrode active material layer 12 may contain a plurality of types of negative electrode active materials such as carbon-based active materials in addition to silicon-based active material particles. Furthermore, other materials such as a thickener (also referred to as “binder” or “binder”) or a conductive aid may be included in battery design. The shape of the negative electrode active material may be particulate.

上述のように、本発明の負極活物質は、ＳｉＯｘ（０．５≦ｘ≦１．６）からなるケイ素系活物質粒子を含む。このケイ素系活物質粒子は酸化ケイ素材（ＳｉＯｘ：０．５≦ｘ≦１．６）であり、その組成としてはｘが１に近い方が好ましい。これは、高いサイクル特性が得られるからである。なお、本発明における酸化ケイ素材の組成は必ずしも純度１００％を意味しているわけではなく、微量の不純物元素やＬｉを含んでいても良い。 As described above, the negative electrode active material of the present invention includes silicon-based active material particles made of SiO x (0.5 ≦ x ≦ 1.6). The silicon-based active material particles are a silicon oxide material (SiO x : 0.5 ≦ x ≦ 1.6), and the composition is preferably such that x is close to 1. This is because high cycle characteristics can be obtained. The composition of the silicon oxide material in the present invention does not necessarily mean 100% purity, and may contain a small amount of impurity elements and Li.

また、本発明において、ケイ素化合物の結晶性は低いほどよい。具体的には、ケイ素系活物質のＸ線回折により得られる（１１１）結晶面に起因する回折ピークの半値幅（２θ）が１．２°以上であるとともに、その結晶面に起因する結晶子サイズが７．５ｎｍ以下であることが望ましい。このように、特に結晶性が低くＳｉ結晶の存在量が少ないことにより、電池特性を向上させるだけでなく、安定的なＬｉ化合物の生成をすることができる。   In the present invention, the lower the crystallinity of the silicon compound, the better. Specifically, the full width at half maximum (2θ) of a diffraction peak attributed to a (111) crystal plane obtained by X-ray diffraction of a silicon-based active material is 1.2 ° or more, and a crystallite attributed to the crystal plane It is desirable that the size is 7.5 nm or less. As described above, since the crystallinity is low and the amount of Si crystals present is small, not only the battery characteristics are improved, but also a stable Li compound can be generated.

また、ケイ素化合物のメディアン径は特に限定されないが、中でも０．５μｍ以上１５μｍ以下であることが好ましい。この範囲であれば、充放電時においてリチウムイオンの吸蔵放出がされやすくなるとともに、ケイ素系活物質粒子が割れにくくなるからである。このメディアン径が０．５μｍ以上であれば、表面積が大きすぎないため、充放電時に副反応を起こしにくく、電池不可逆容量を低減することができる。一方、メディアン径が１５μｍ以下であれば、ケイ素系活物質粒子が割れにくく新生面が出にくいため好ましい。   Further, the median diameter of the silicon compound is not particularly limited, but it is preferably 0.5 μm or more and 15 μm or less. This is because, within this range, it is easy to occlude and release lithium ions during charging and discharging, and the silicon-based active material particles are difficult to break. If the median diameter is 0.5 μm or more, the surface area is not too large, so that side reactions are unlikely to occur during charging and discharging, and the battery irreversible capacity can be reduced. On the other hand, a median diameter of 15 μm or less is preferable because the silicon-based active material particles are difficult to break and a new surface is difficult to appear.

更に、本発明において、ケイ素系活物質は、ケイ素化合物に含まれるＬｉ化合物として、Ｌｉ２ＳｉＯ３が存在するものであることが好ましい。Ｌｉ２ＳｉＯ３のようなＬｉシリケートは、他のＬｉ化合物よりも比較的安定しているため、これらのＬｉ化合物を含むケイ素系活物質は、より安定した電池特性を得ることができる。これらのＬｉ化合物は、ケイ素化合物の内部に生成するＳｉＯ２成分の一部をＬｉ化合物へ選択的に変更し、ケイ素化合物を改質することにより得ることができる。 Furthermore, in the present invention, it is preferable that the silicon-based active material includes Li 2 SiO 3 as a Li compound contained in the silicon compound. Since Li silicate such as Li 2 SiO 3 is relatively more stable than other Li compounds, a silicon-based active material containing these Li compounds can obtain more stable battery characteristics. These Li compounds can be obtained by selectively changing a part of the SiO 2 component generated inside the silicon compound to the Li compound and modifying the silicon compound.

ケイ素化合物の内部のＬｉ化合物はＮＭＲ（核磁気共鳴）とＸＰＳ（Ｘ線光電子分光）で定量可能である。ＸＰＳとＮＭＲの測定は、例えば、以下の条件により行うことができる。
ＸＰＳ
・装置： Ｘ線光電子分光装置、
・Ｘ線源： 単色化Ａｌ Ｋα線、
・Ｘ線スポット径： １００μｍ、
・Ａｒイオン銃スパッタ条件： ０．５ｋＶ ２ｍｍ×２ｍｍ。
２９Ｓｉ ＭＡＳ ＮＭＲ（マジック角回転核磁気共鳴）
・装置： Ｂｒｕｋｅｒ社製７００ＮＭＲ分光器、
・プローブ： ４ｍｍＨＲ−ＭＡＳローター ５０μＬ、
・試料回転速度： １０ｋＨｚ、
・測定環境温度： ２５℃。 The Li compound inside the silicon compound can be quantified by NMR (nuclear magnetic resonance) and XPS (X-ray photoelectron spectroscopy). The XPS and NMR measurements can be performed, for example, under the following conditions.
XPS
・ Device: X-ray photoelectron spectrometer,
・ X-ray source: Monochromatic Al Kα ray,
・ X-ray spot diameter: 100 μm,
Ar ion gun sputtering conditions: 0.5 kV 2 mm × 2 mm.
29 Si MAS NMR (magic angle rotating nuclear magnetic resonance)
Apparatus: 700 NMR spectrometer manufactured by Bruker,
Probe: 4 mm HR-MAS rotor 50 μL,
Sample rotation speed: 10 kHz,
-Measurement environment temperature: 25 ° C.

また、本発明において、ケイ素化合物の改質を行う際に、電気化学的手法や、酸化還元反応による改質、及び物理的手法である熱ドープ等の手法を用いることができる。特に、電気化学的手法及び酸化還元による改質を用いてケイ素化合物を改質した場合、負極活物質の電池特性が向上する。また、改質では、ケイ素化合物へのＬｉの挿入だけでなく、ケイ素化合物からのＬｉの脱離を合わせて行うと良い。これにより、負極活物質の耐水性などといったスラリーに対する安定性がより向上する。   Further, in the present invention, when a silicon compound is modified, an electrochemical method, a modification by oxidation-reduction reaction, and a physical method such as thermal doping can be used. In particular, when the silicon compound is modified using an electrochemical technique and oxidation-reduction modification, the battery characteristics of the negative electrode active material are improved. Further, the modification may be performed not only by inserting Li into the silicon compound but also by detaching Li from the silicon compound. Thereby, stability with respect to slurry, such as water resistance of a negative electrode active material, improves more.

また、本発明の負極活物質では、ケイ素化合物が、２９Ｓｉ−ＭＡＳ−ＮＭＲ スペクトルから得られるケミカルシフト値として−９５〜−１５０ｐｐｍに与えられるＳｉＯ２領域に由来するピークを持つことが好ましい。このように、改質によってケイ素化合物中のＳｉＯ２領域を全て、Ｌｉ化合物に変更せずに、ある程度ＳｉＯ２領域を残しておくことで、スラリーに対する安定性がより向上する。 Further, the negative electrode active material of the present invention, the silicon compound preferably has a peak derived from a SiO 2 region given to -95-150 ppm as chemical shift values obtained from the 29 Si-MAS-NMR spectra. In this way, the stability to the slurry is further improved by leaving the SiO 2 region to some extent without changing all the SiO 2 regions in the silicon compound to the Li compound by the modification.

また、本発明の負極活物質では、ケイ素化合物が、２９Ｓｉ−ＭＡＳ−ＮＭＲ スペクトルから得られるケミカルシフト値として−７５ｐｐｍ付近に与えられるＬｉ２ＳｉＯ３に由来するピークの強度Ａと、−９５〜−１５０ｐｐｍに与えられるＳｉＯ２領域に由来するピークの強度Ｂとが、Ａ＞Ｂの関係を満たすことが好ましい。ケイ素化合物中において、ＳｉＯ２成分を基準とした場合にＬｉ２ＳｉＯ３の量が比較的多いものであれば、Ｌｉの挿入による電池特性の向上効果を十分に得られる。 Further, in the negative electrode active material of the present invention, the silicon compound has a peak intensity A derived from Li 2 SiO 3 given in the vicinity of −75 ppm as a chemical shift value obtained from a 29 Si-MAS-NMR spectrum, and −95 to It is preferable that the intensity B of the peak derived from the SiO 2 region given at −150 ppm satisfies the relationship of A> B. In the silicon compound, if the amount of Li 2 SiO 3 is relatively large when the SiO 2 component is used as a reference, the effect of improving battery characteristics by inserting Li can be sufficiently obtained.

また、上述のように、ケイ素系活物質粒子はケイ素化合物の表面や炭素被膜の表面に、非晶質の金属酸化物及び金属水酸化物から成る複合体を含む複合層を有する。   Further, as described above, the silicon-based active material particles have a composite layer including a composite made of an amorphous metal oxide and a metal hydroxide on the surface of the silicon compound or the surface of the carbon coating.

特に、金属酸化物及び金属水酸化物から成る複合体は、金属アルコキシドの加水分解・脱水縮合によって生成されたものであることが好ましい。これは、複合層内に金属酸化物領域と水酸化物領域が両立するからである。   In particular, the composite composed of a metal oxide and a metal hydroxide is preferably produced by hydrolysis / dehydration condensation of a metal alkoxide. This is because the metal oxide region and the hydroxide region are compatible in the composite layer.

金属酸化物及び金属水酸化物は、アルミニウム、マグネシウム、チタニウム、及びジルコニウムのうち少なくとも１種の元素を含むことが好ましい。   The metal oxide and metal hydroxide preferably contain at least one element of aluminum, magnesium, titanium, and zirconium.

特に、複合層の最表層部はＡｌ（ＯＨ）３に近い構造を有するものであることが好ましい。これは、負極作製時に、スラリーがより安定するからである。 In particular, it is preferable that the outermost layer portion of the composite layer has a structure close to Al (OH) 3 . This is because the slurry becomes more stable during the production of the negative electrode.

また、アルミニウムイソプロポキシドのゾルゲル反応処理によって、複合層を形成することが特に好ましい。このような方法であれば、ケイ素系活物質の表層に非晶質のアルミニウム酸化物及びアルミニウム水酸化物から成る複合体を含む、薄い複合層を形成できる。   Further, it is particularly preferable to form a composite layer by a sol-gel reaction treatment of aluminum isopropoxide. With such a method, a thin composite layer including a composite composed of amorphous aluminum oxide and aluminum hydroxide can be formed on the surface layer of the silicon-based active material.

また、複合層の厚さは１０ｎｍ以下であることが好ましく、さらに、５ｎｍ以下であることがより好ましい。複合層の厚さが１０ｎｍ以下であれば、合剤組成にもよるが、電気抵抗が高くなり過ぎないため、電池特性が向上する。また、膜厚が２〜３ｎｍ程度であると、電気抵抗の増加を抑制しつつ、スラリーに対する安定性をより向上させることができる。なお、複合層の膜厚はＴＥＭ（透過型電子顕微鏡）により確認可能である。   Further, the thickness of the composite layer is preferably 10 nm or less, and more preferably 5 nm or less. If the thickness of the composite layer is 10 nm or less, although it depends on the composition of the mixture, the electric resistance does not become too high, so that the battery characteristics are improved. Moreover, the stability with respect to a slurry can be improved more, suppressing the increase in an electrical resistance as a film thickness is about 2-3 nm. The film thickness of the composite layer can be confirmed with a TEM (transmission electron microscope).

またこのとき、本発明の負極活物質と炭素系活物質とを混合した負極活物質を使用して作製した負極電極と対極リチウムとから成る試験セルを充放電し、放電容量Ｑを対極リチウムを基準とする負極電極の電位Ｖで微分した微分値ｄＱ／ｄＶと電位Ｖとの関係を示すグラフを描いた場合に、負極活物質がリチウムを脱離するよう電流を流す放電時における、負極電極の電位Ｖが０．４０Ｖ〜０．５５Ｖの範囲にピークを有するものであることが好ましい。Ｖ−ｄＱ／ｄＶ曲線における上記のピークはケイ素材のピークと類似しており、より高電位側における放電カーブが鋭く立ち上がるため、電池設計を行う際、容量発現しやすくなる。   At this time, a test cell composed of a negative electrode and a counter electrode lithium prepared by using the negative electrode active material obtained by mixing the negative electrode active material and the carbon-based active material of the present invention was charged and discharged, and the discharge capacity Q was changed to the counter electrode lithium. When a graph showing the relationship between the differential value dQ / dV differentiated by the potential V of the reference negative electrode and the potential V is drawn, the negative electrode at the time of discharge in which a current flows so that the negative electrode active material desorbs lithium It is preferable that the potential V has a peak in the range of 0.40V to 0.55V. The above peak in the V-dQ / dV curve is similar to the peak of the siliceous material, and the discharge curve on the higher potential side rises sharply, so that the capacity is easily developed when designing the battery.

［負極の製造方法］
続いて、本発明の非水電解質二次電池の負極の製造方法の一例を説明する。 [Production method of negative electrode]
Then, an example of the manufacturing method of the negative electrode of the nonaqueous electrolyte secondary battery of this invention is demonstrated.

最初に負極に含まれる負極材の製造方法を説明する。まず、ＳｉＯｘ（０．５≦ｘ≦１．６）で表される酸化珪素粒子を作製する。次に、酸化珪素粒子の表面に炭素被膜を形成する。次に、酸化珪素粒子にＬｉを挿入、脱離することにより、酸化珪素粒子を改質する。このとき、同時に酸化珪素粒子の内部や表面にＬｉ化合物を生成させることができる。そして、改質後の酸化珪素粒子の表面に、非晶質の金属酸化物及び金属水酸化物から成る複合体を含む複合層を形成する。そしてこのような酸化珪素粒子を負極活物質粒子として用いて、導電助剤やバインダと混合するなどして、負極材及び負極電極を製造できる。 First, a method for producing a negative electrode material included in the negative electrode will be described. First, silicon oxide particles represented by SiO x (0.5 ≦ x ≦ 1.6) are produced. Next, a carbon film is formed on the surface of the silicon oxide particles. Next, the silicon oxide particles are modified by inserting and removing Li from the silicon oxide particles. At the same time, a Li compound can be generated inside or on the surface of the silicon oxide particles. Then, a composite layer including a composite made of an amorphous metal oxide and a metal hydroxide is formed on the surface of the modified silicon oxide particles. Then, using such silicon oxide particles as negative electrode active material particles, a negative electrode material and a negative electrode can be produced by mixing with a conductive additive or a binder.

より具体的には、負極材は、例えば、以下の手順により製造される。   More specifically, the negative electrode material is manufactured by the following procedure, for example.

まず、酸化珪素ガスを発生する原料を不活性ガスの存在下もしくは減圧下９００℃〜１６００℃の温度範囲で加熱し、酸化ケイ素ガスを発生させる。この場合、原料は金属珪素粉末と二酸化珪素粉末との混合であり、金属珪素粉末の表面酸素及び反応炉中の微量酸素の存在を考慮すると、混合モル比が、０．８＜金属珪素粉末／二酸化珪素粉末＜１．３の範囲であることが望ましい。粒子中のＳｉ結晶子は仕込み範囲や気化温度の変更、また生成後の熱処理で制御される。発生したガスは吸着板に堆積される。反応炉内温度を１００℃以下に下げた状態で堆積物を取出し、ボールミル、ジェットミルなどを用いて粉砕、粉末化を行う。   First, a raw material that generates silicon oxide gas is heated in a temperature range of 900 ° C. to 1600 ° C. in the presence of an inert gas or under reduced pressure to generate silicon oxide gas. In this case, the raw material is a mixture of metal silicon powder and silicon dioxide powder, and considering the surface oxygen of the metal silicon powder and the presence of trace amounts of oxygen in the reactor, the mixing molar ratio is 0.8 <metal silicon powder / It is desirable that the silicon dioxide powder is in the range of <1.3. The Si crystallites in the particles are controlled by changing the preparation range and vaporization temperature, and by heat treatment after generation. The generated gas is deposited on the adsorption plate. The deposit is taken out with the temperature in the reactor lowered to 100 ° C. or lower, and pulverized and powdered using a ball mill, a jet mill or the like.

次に、得られた粉末材料（ケイ素化合物）の表層に炭素被膜を形成する。炭素被膜は、負極活物質の電池特性をより向上させるには効果的である。   Next, a carbon film is formed on the surface layer of the obtained powder material (silicon compound). The carbon coating is effective for further improving the battery characteristics of the negative electrode active material.

粉末材料の表層に炭素被膜を形成する手法としては、熱分解ＣＶＤが望ましい。熱分解ＣＶＤは炉内に酸化ケイ素粉末をセットし、炉内に炭化水素ガスを充満させ炉内温度を昇温させる。分解温度は特に限定しないが特に１２００℃以下が望ましい。より望ましいのは９５０℃以下であり、意図しないケイ素酸化物の不均化を抑制することが可能である。炭化水素ガスは特に限定することはないが、ＣｎＨｍ組成のうち３≧ｎが望ましい。低製造コスト及び分解生成物の物性が良いからである。 Pyrolysis CVD is desirable as a method for forming a carbon film on the surface layer of the powder material. In pyrolysis CVD, silicon oxide powder is set in a furnace, the furnace is filled with hydrocarbon gas, and the temperature in the furnace is raised. The decomposition temperature is not particularly limited, but is particularly preferably 1200 ° C. or lower. More desirably, the temperature is 950 ° C. or lower, and unintended disproportionation of silicon oxide can be suppressed. Hydrocarbon gas is not particularly limited, 3 ≧ n of C n H m composition it is desirable. This is because the low production cost and the physical properties of the decomposition products are good.

次に、粉末材料のバルク内の改質を行う。バルク内改質は電気化学的にＬｉを挿入・脱離し得る装置を用いて行うことが望ましい。特に装置構造を限定することはないが、例えば図３に示すバルク内改質装置２０を用いて、バルク内改質を行うことができる。バルク内改質装置２０は、有機溶媒２３で満たされた浴槽２７と、浴槽２７内に配置され、電源２６の一方に接続された陽電極（リチウム源、改質源）２１と、浴槽２７内に配置され、電源２６の他方に接続された粉末格納容器２５と、陽電極２１と粉末格納容器２５との間に設けられたセパレータ２４とを有している。粉末格納容器２５には、酸化ケイ素の粉末２２が格納される。そして、粉末格納容器には、ケイ素化合物（酸化珪素粒子）を格納し、電源により酸化珪素粒子を格納した粉末格納容器と陽電極（リチウム源）に電圧をかける。これにより、酸化珪素粒子にリチウムを挿入、脱離することができるため、酸化珪素の粉末２２を改質できる。   Next, modification in the bulk of the powder material is performed. In-bulk reforming is desirably performed using an apparatus capable of electrochemically inserting and extracting Li. Although the apparatus structure is not particularly limited, for example, the bulk reforming can be performed using the bulk reforming apparatus 20 shown in FIG. The in-bulk reformer 20 includes a bathtub 27 filled with an organic solvent 23, a positive electrode (lithium source, reforming source) 21 disposed in the bathtub 27 and connected to one of the power sources 26, And a separator 24 provided between the positive electrode 21 and the powder storage container 25. The powder storage container 25 is connected to the other side of the power source 26. The powder storage container 25 stores silicon oxide powder 22. A silicon compound (silicon oxide particles) is stored in the powder storage container, and a voltage is applied to the powder storage container and the positive electrode (lithium source) storing the silicon oxide particles by a power source. Thereby, since lithium can be inserted into and desorbed from the silicon oxide particles, the silicon oxide powder 22 can be modified.

浴槽２７内の有機溶媒２３として、炭酸エチレン、炭酸プロピレン、炭酸ジメチル、炭酸ジエチル、炭酸エチルメチル、炭酸フルオロメチルメチル、炭酸ジフルオロメチルメチルなどを用いることができる。また、有機溶媒２３に含まれる電解質塩として、六フッ化リン酸リチウム（ＬｉＰＦ６）、四フッ化ホウ酸リチウム（ＬｉＢＦ４）などを用いることができる。 As the organic solvent 23 in the bathtub 27, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoromethyl methyl carbonate, difluoromethyl methyl carbonate, or the like can be used. As the electrolyte salt contained in the organic solvent 23, lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), or the like can be used.

陽電極２１はＬｉ箔を用いてもよく、また、Ｌｉ含有化合物を用いてもよい。Ｌｉ含有化合物として、炭酸リチウム、酸化リチウム、コバルト酸リチウム、オリビン鉄リチウム、ニッケル酸リチウム、リン酸バナジウムリチウムなどがあげられる。   The positive electrode 21 may use a Li foil or a Li-containing compound. Examples of the Li-containing compound include lithium carbonate, lithium oxide, lithium cobaltate, lithium olivine, lithium nickelate, and lithium vanadium phosphate.

また、改質は熱ドープ法を使用して行っても良い。この場合、例えば、粉末材料をＬｉＨ粉やＬｉ粉と混合し、非酸化雰囲気下で加熱をすることで改質可能である。非酸化雰囲気としては、例えば、Ａｒ雰囲気などが使用できる。より具体的には、まず、Ａｒ雰囲気下でＬｉＨ粉又はＬｉ粉と酸化珪素粉末を十分に混ぜ、封止を行い、封止した容器ごと撹拌することで均一化する。その後、７００℃〜７５０℃の範囲で加熱し改質を行う。またこの場合、Ｌｉをケイ素化合物から脱離するには、加熱後の粉末を十分に冷却し、その後アルコールやアルカリ水、弱酸や純水で洗浄する方法などを使用できる。   Further, the modification may be performed using a thermal doping method. In this case, for example, the powder material can be modified by mixing with LiH powder or Li powder and heating in a non-oxidizing atmosphere. For example, an Ar atmosphere can be used as the non-oxidizing atmosphere. More specifically, first, LiH powder or Li powder and silicon oxide powder are sufficiently mixed in an Ar atmosphere, sealed, and homogenized by stirring the sealed container. Thereafter, the reforming is performed by heating in the range of 700 ° C to 750 ° C. In this case, in order to desorb Li from the silicon compound, a method of sufficiently cooling the heated powder and then washing with alcohol, alkaline water, weak acid or pure water can be used.

続いて、改質後の酸化珪素粒子の表面に、非晶質の金属酸化物及び金属水酸化物から成る複合体を含む複合層を形成する。複合層は、金属アルコキシドの加水分解及び脱水縮合によって形成することが好ましい。このようにすれば、金属アルコキシドの加水分解・脱水縮合が連続して起こることで、金属酸化物領域と金属水酸化物領域が両立するように複合体を効率よく生成することができる。より具体的には、例えば、以下のような手順で複合層を形成できる。   Subsequently, a composite layer including a composite made of an amorphous metal oxide and a metal hydroxide is formed on the surface of the modified silicon oxide particles. The composite layer is preferably formed by hydrolysis and dehydration condensation of a metal alkoxide. If it does in this way, a hydrolysis and dehydration condensation of a metal alkoxide will occur continuously, and a complex can be efficiently generated so that a metal oxide field and a metal hydroxide field may be compatible. More specifically, for example, the composite layer can be formed by the following procedure.

まず、脱水エタノールと、脱水エタノールの質量の四分の一の質量分の改質後のケイ素化合物と改質後のケイ素化合物の１．５質量％相当のＡｌイソプロポキシドを容器に投入し、３時間半撹拌する。撹拌後は吸引濾過でエタノールを除去し、ケイ素化合物を、１２０℃で１２時間真空乾燥する。この時、複合層の膜厚は改質材と同時に添加するＡｌイソプロポキシドの質量を変えることで制御可能である。   First, dehydrated ethanol, a silicon compound after modification of a mass of a quarter of the mass of dehydrated ethanol, and Al isopropoxide equivalent to 1.5% by mass of the modified silicon compound are put into a container, Stir for 3.5 hours. After stirring, ethanol is removed by suction filtration, and the silicon compound is vacuum-dried at 120 ° C. for 12 hours. At this time, the film thickness of the composite layer can be controlled by changing the mass of Al isopropoxide added simultaneously with the modifier.

続いて、上記の複合層を有する酸化珪素粒子を含むケイ素系活物質と必要に応じて炭素系活物質を混合するとともに、これらの負極活物質とバインダ、導電助剤など他の材料とを混合し負極合剤としたのち、有機溶剤又は水などを加えてスラリーとする。   Subsequently, a silicon-based active material containing silicon oxide particles having the above composite layer and, if necessary, a carbon-based active material are mixed, and these negative electrode active materials are mixed with other materials such as a binder and a conductive additive. After forming the negative electrode mixture, an organic solvent or water is added to form a slurry.

次に、図２に示したように、負極集電体１１の表面に、この負極合剤のスラリーを塗布し、乾燥させて、負極活物質層１２を形成する。この時、必要に応じて加熱プレスなどを行っても良い。以上のようにして、本発明の非水電解質二次電池の負極を製造することができる。   Next, as shown in FIG. 2, the negative electrode mixture slurry is applied to the surface of the negative electrode current collector 11 and dried to form the negative electrode active material layer 12. At this time, a heating press or the like may be performed as necessary. As described above, the negative electrode of the nonaqueous electrolyte secondary battery of the present invention can be produced.

＜リチウムイオン二次電池＞
次に、上記した本発明の非水電解質二次電池の具体例として、ラミネートフィルム型のリチウムイオン二次電池について説明する。 <Lithium ion secondary battery>
Next, a laminated film type lithium ion secondary battery will be described as a specific example of the nonaqueous electrolyte secondary battery of the present invention.

［ラミネートフィルム型二次電池の構成］
図４に示すラミネートフィルム型のリチウムイオン二次電池３０は、主にシート状の外装部材３５の内部に巻回電極体３１が収納されたものである。この巻回電極体３１は正極、負極間にセパレータを有し、巻回されたものである。また正極、負極間にセパレータを有し積層体を収納した場合も存在する。どちらの電極体においても、正極に正極リード３２が取り付けられ、負極に負極リード３３が取り付けられている。電極体の最外周部は保護テープにより保護されている。 [Configuration of laminated film type secondary battery]
A laminated film type lithium ion secondary battery 30 shown in FIG. 4 is one in which a wound electrode body 31 is accommodated mainly in a sheet-like exterior member 35. The wound electrode body 31 has a separator between a positive electrode and a negative electrode, and is wound. There is also a case where a separator is provided between the positive electrode and the negative electrode and a laminate is accommodated. In both electrode bodies, the positive electrode lead 32 is attached to the positive electrode, and the negative electrode lead 33 is attached to the negative electrode. The outermost peripheral part of the electrode body is protected by a protective tape.

正負極リード３２、３３は、例えば、外装部材３５の内部から外部に向かって一方向で導出されている。正極リード３２は、例えば、アルミニウムなどの導電性材料により形成され、負極リード３３は、例えば、ニッケル、銅などの導電性材料により形成される。   The positive and negative leads 32 and 33 are led out in one direction from the inside of the exterior member 35 to the outside, for example. The positive electrode lead 32 is formed of a conductive material such as aluminum, and the negative electrode lead 33 is formed of a conductive material such as nickel or copper.

外装部材３５は、例えば、融着層、金属層、表面保護層がこの順に積層されたラミネートフィルムであり、このラミネートフィルムは融着層が電極体３１と対向するように、２枚のフィルムの融着層における外周縁部同士が融着、又は、接着剤などで張り合わされている。融着部は、例えばポリエチレンやポリプロピレンなどのフィルムであり、金属部はアルミ箔などである。保護層は例えば、ナイロンなどである。   The exterior member 35 is, for example, a laminate film in which a fusion layer, a metal layer, and a surface protective layer are laminated in this order. This laminate film is formed of two films so that the fusion layer faces the electrode body 31. The outer peripheral edges of the fusion layer are bonded together with an adhesive or an adhesive. The fused part is, for example, a film such as polyethylene or polypropylene, and the metal part is aluminum foil or the like. The protective layer is, for example, nylon.

外装部材３５と正負極リードとの間には、外気侵入防止のため密着フィルム３４が挿入されている。この材料は、例えば、ポリエチレン、ポリプロピレン、ポリオレフィン樹脂である。   An adhesion film 34 is inserted between the exterior member 35 and the positive and negative electrode leads to prevent intrusion of outside air. This material is, for example, polyethylene, polypropylene, or polyolefin resin.

正極は、例えば、図２の負極１０と同様に、正極集電体の両面又は片面に正極活物質層を有している。   The positive electrode has, for example, a positive electrode active material layer on both surfaces or one surface of the positive electrode current collector, similarly to the negative electrode 10 of FIG.

正極集電体は、例えば、アルミニウムなどの導電性材により形成されている。   The positive electrode current collector is formed of, for example, a conductive material such as aluminum.

正極活物質層は、リチウムイオンの吸蔵放出可能な正極材のいずれか１種又は２種以上を含んでおり、設計に応じて正極結着剤、正極導電助剤、分散剤などの他の材料を含んでいても良い。この場合、正極結着剤、正極導電助剤に関する詳細は、例えば既に記述した負極結着剤、負極導電助剤と同様である。   The positive electrode active material layer includes any one or more of positive electrode materials capable of occluding and releasing lithium ions, and other materials such as a positive electrode binder, a positive electrode conductive additive, and a dispersant depending on the design. May be included. In this case, details regarding the positive electrode binder and the positive electrode conductive additive are the same as, for example, the negative electrode binder and negative electrode conductive additive already described.

正極材料としては、リチウム含有化合物が望ましい。このリチウム含有化合物は、例えばリチウムと遷移金属元素からなる複合酸化物、又はリチウムと遷移金属元素を有するリン酸化合物があげられる。これらの正極材の中でもニッケル、鉄、マンガン、コバルトの少なくとも１種以上を有する化合物が好ましい。これらの化学式として、例えば、ＬｉｘＭ１Ｏ２あるいはＬｉｙＭ２ＰＯ４で表される。式中、Ｍ１、Ｍ２は少なくとも１種以上の遷移金属元素を示す。ｘ、ｙの値は電池充放電状態によって異なる値を示すが、一般的に０．０５≦ｘ≦１．１０、０．０５≦ｙ≦１．１０で示される。 As the positive electrode material, a lithium-containing compound is desirable. Examples of the lithium-containing compound include a composite oxide composed of lithium and a transition metal element, or a phosphate compound having lithium and a transition metal element. Among these positive electrode materials, compounds having at least one of nickel, iron, manganese and cobalt are preferable. These chemical formulas are represented by, for example, Li x M 1 O 2 or Li y M 2 PO 4 . In the formula, M 1 and M 2 represent at least one transition metal element. The values of x and y vary depending on the battery charge / discharge state, but are generally expressed as 0.05 ≦ x ≦ 1.10 and 0.05 ≦ y ≦ 1.10.

リチウムと遷移金属元素とを有する複合酸化物としては、例えば、リチウムコバルト複合酸化物（ＬｉｘＣｏＯ２）、リチウムニッケル複合酸化物（ＬｉｘＮｉＯ２）、リチウムニッケルコバルト複合酸化物などが挙げられる。リチウムニッケルコバルト複合酸化物としては、例えばリチウムニッケルコバルトアルミニウム複合酸化物（ＮＣＡ）やリチウムニッケルコバルトマンガン複合酸化物（ＮＣＭ）などが挙げられる。 Examples of the composite oxide having lithium and a transition metal element include lithium cobalt composite oxide (Li x CoO 2 ), lithium nickel composite oxide (Li x NiO 2 ), and lithium nickel cobalt composite oxide. . Examples of the lithium nickel cobalt composite oxide include lithium nickel cobalt aluminum composite oxide (NCA) and lithium nickel cobalt manganese composite oxide (NCM).

リチウムと遷移金属元素とを有するリン酸化合物としては、例えば、リチウム鉄リン酸化合物（ＬｉＦｅＰＯ４）あるいはリチウム鉄マンガンリン酸化合物（ＬｉＦｅ１−ｕＭｎｕＰＯ４（０＜ｕ＜１））などが挙げられる。これらの正極材を用いれば、高い電池容量を得ることができるとともに、優れたサイクル特性も得ることができる。 Examples of the phosphate compound having lithium and a transition metal element include a lithium iron phosphate compound (LiFePO 4 ) or a lithium iron manganese phosphate compound (LiFe 1-u Mn u PO 4 (0 <u <1)). Is mentioned. If these positive electrode materials are used, a high battery capacity can be obtained, and excellent cycle characteristics can also be obtained.

［負極］
負極は、上記した図２のリチウムイオン二次電池用負極１０と同様の構成を有し、例えば、集電体の両面に負極活物質層を有している。この負極は、正極活物質剤から得られる電気容量（電池としての充電容量）に対して、負極充電容量が大きくなることが好ましい。これにより、負極上でのリチウム金属の析出を抑制することができる。 [Negative electrode]
The negative electrode has the same configuration as the negative electrode 10 for lithium ion secondary battery in FIG. 2 described above, and has, for example, a negative electrode active material layer on both surfaces of the current collector. This negative electrode preferably has a negative electrode charge capacity larger than the electric capacity (charge capacity as a battery) obtained from the positive electrode active material agent. Thereby, precipitation of lithium metal on the negative electrode can be suppressed.

正極活物質層は、正極集電体の両面の一部に設けられており、同様に負極活物質層も負極集電体の両面の一部に設けられている。この場合、例えば、負極集電体上に設けられた負極活物質層は対向する正極活物質層が存在しない領域が設けられている。これは、安定した電池設計を行うためである。   The positive electrode active material layer is provided on part of both surfaces of the positive electrode current collector, and similarly, the negative electrode active material layer is provided on part of both surfaces of the negative electrode current collector. In this case, for example, the negative electrode active material layer provided on the negative electrode current collector is provided with a region where there is no opposing positive electrode active material layer. This is to perform a stable battery design.

上記の負極活物質層と正極活物質層とが対向しない領域では、充放電の影響をほとんど受けることが無い。そのため、負極活物質層の状態が形成直後のまま維持され、これによって負極活物質の組成などを、充放電の有無に依存せずに再現性良く正確に調べることができる。   In the region where the negative electrode active material layer and the positive electrode active material layer do not face each other, there is almost no influence of charge / discharge. Therefore, the state of the negative electrode active material layer is maintained as it is immediately after formation, whereby the composition of the negative electrode active material can be accurately examined with good reproducibility without depending on the presence or absence of charge / discharge.

［セパレータ］
セパレータは正極と負極を隔離し、両極接触に伴う電流短絡を防止しつつ、リチウムイオンを通過させるものである。このセパレータは、例えば合成樹脂、あるいはセラミックからなる多孔質膜により形成されており、２種以上の多孔質膜が積層された積層構造を有しても良い。合成樹脂として例えば、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレンなどが挙げられる。 [Separator]
The separator separates the positive electrode and the negative electrode, and allows lithium ions to pass through while preventing a short circuit due to contact between the two electrodes. This separator is formed of, for example, a porous film made of synthetic resin or ceramic, and may have a laminated structure in which two or more kinds of porous films are laminated. Examples of the synthetic resin include polytetrafluoroethylene, polypropylene, and polyethylene.

［電解液］
活物質層の少なくとも一部、又は、セパレータには、液状の電解質（電解液）が含浸されている。この電解液は、溶媒中に電解質塩が溶解されており、添加剤など他の材料を含んでいても良い。 [Electrolyte]
At least a part of the active material layer or the separator is impregnated with a liquid electrolyte (electrolytic solution). This electrolytic solution has an electrolyte salt dissolved in a solvent, and may contain other materials such as additives.

溶媒は、例えば、非水溶媒を用いることができる。非水溶媒としては、例えば、炭酸エチレン、炭酸プロピレン、炭酸ブチレン、炭酸ジメチル、炭酸ジエチル、炭酸エチルメチル、炭酸メチルプロピル、１，２−ジメトキシエタン、又はテトラヒドロフランなどが挙げられる。この中でも、炭酸エチレン、炭酸プロピレン、炭酸ジメチル、炭酸ジエチル、炭酸エチルメチルのうちの少なくとも１種以上を用いることが望ましい。より良い特性が得られるからである。またこの場合、炭酸エチレン、炭酸プロピレンなどの高粘度溶媒と、炭酸ジメチル、炭酸エチルメチル、炭酸ジエチルなどの低粘度溶媒を組み合わせることにより、より優位な特性を得ることができる。これは、電解質塩の解離性やイオン移動度が向上するためである。   For example, a non-aqueous solvent can be used as the solvent. Examples of the non-aqueous solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, 1,2-dimethoxyethane, and tetrahydrofuran. Among these, it is desirable to use at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. This is because better characteristics can be obtained. In this case, more advantageous characteristics can be obtained by combining a high viscosity solvent such as ethylene carbonate or propylene carbonate and a low viscosity solvent such as dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate. This is because the dissociation property and ion mobility of the electrolyte salt are improved.

溶媒添加物として、不飽和炭素結合環状炭酸エステルを含んでいることが好ましい。充放電時に負極表面に安定な被膜が形成され、電解液の分解反応が抑制できるからである。不飽和炭素結合環状炭酸エステルとして、例えば炭酸ビニレン又は炭酸ビニルエチレンなどが挙げられる。   The solvent additive preferably contains an unsaturated carbon bond cyclic carbonate. This is because a stable film is formed on the surface of the negative electrode during charging and discharging, and the decomposition reaction of the electrolytic solution can be suppressed. Examples of the unsaturated carbon bond cyclic ester carbonate include vinylene carbonate and vinyl ethylene carbonate.

また溶媒添加物として、スルトン（環状スルホン酸エステル）を含んでいることが好ましい。電池の化学的安定性が向上するからである。スルトンとしては、例えばプロパンスルトン、プロペンスルトンが挙げられる。   The solvent additive preferably contains sultone (cyclic sulfonic acid ester). This is because the chemical stability of the battery is improved. Examples of sultone include propane sultone and propene sultone.

さらに、溶媒は、酸無水物を含んでいることが好ましい。電解液の化学的安定性が向上するからである。酸無水物としては、例えば、プロパンジスルホン酸無水物が挙げられる。   Furthermore, it is preferable that the solvent contains an acid anhydride. This is because the chemical stability of the electrolytic solution is improved. Examples of the acid anhydride include propanedisulfonic acid anhydride.

電解質塩は、例えば、リチウム塩などの軽金属塩のいずれか１種類以上含むことができる。リチウム塩として、例えば、六フッ化リン酸リチウム（ＬｉＰＦ６）、四フッ化ホウ酸リチウム（ＬｉＢＦ４）などが挙げられる。   The electrolyte salt can contain, for example, any one or more of light metal salts such as lithium salts. Examples of the lithium salt include lithium hexafluorophosphate (LiPF6) and lithium tetrafluoroborate (LiBF4).

電解質塩の含有量は、溶媒に対して０．５ｍｏｌ／ｋｇ以上２．５ｍｏｌ／ｋｇ以下であることが好ましい。これは、高いイオン伝導性が得られるからである。   The content of the electrolyte salt is preferably 0.5 mol / kg or more and 2.5 mol / kg or less with respect to the solvent. This is because high ion conductivity is obtained.

［ラミネートフィルム型二次電池の製造方法］
最初に上記した正極材を用い正極電極を作製する。まず、正極活物質と、必要に応じて正極結着剤、正極導電助剤などを混合し正極合剤としたのち、有機溶剤に分散させ正極合剤スラリーとする。続いて、ナイフロール又はダイヘッドを有するダイコーターなどのコーティング装置で正極集電体に合剤スラリーを塗布し、熱風乾燥させて正極活物質層を得る。最後に、ロールプレス機などで正極活物質層を圧縮成型する。この時、加熱しても良く、また圧縮を複数回繰り返しても良い。 [Production method of laminated film type secondary battery]
First, a positive electrode is manufactured using the positive electrode material described above. First, a positive electrode active material and, if necessary, a positive electrode binder and a positive electrode conductive additive are mixed to form a positive electrode mixture, which is then dispersed in an organic solvent to form a positive electrode mixture slurry. Subsequently, the mixture slurry is applied to the positive electrode current collector with a coating apparatus such as a die coater having a knife roll or a die head, and dried with hot air to obtain a positive electrode active material layer. Finally, the positive electrode active material layer is compression molded with a roll press or the like. At this time, heating may be performed or compression may be repeated a plurality of times.

次に、上記したリチウムイオン二次電池用負極１０の作製と同様の作業手順を用い、負極集電体に負極活物質層を形成し負極を作製する。   Next, a negative electrode is produced by forming a negative electrode active material layer on the negative electrode current collector, using the same operation procedure as the production of the negative electrode 10 for a lithium ion secondary battery described above.

正極及び負極を作製する際に、正極及び負極集電体の両面にそれぞれの活物質層を形成する。この時、どちらの電極においても両面部の活物質塗布長がずれていても良い（図２を参照）。   When producing the positive electrode and the negative electrode, respective active material layers are formed on both surfaces of the positive electrode and the negative electrode current collector. At this time, the active material application length of both surface portions may be shifted in either electrode (see FIG. 2).

続いて、電解液を調整する。続いて、超音波溶接などにより、正極集電体に正極リード３２を取り付けると共に、負極集電体に負極リード３３を取り付ける。続いて、正極と負極とをセパレータを介して積層、又は巻回させて巻回電極体３１を作製し、その最外周部に保護テープを接着させる。次に、扁平な形状となるように巻回体を成型する。続いて、折りたたんだフィルム状の外装部材３５の間に巻回電極体を挟み込んだ後、熱融着法により外装部材の絶縁部同士を接着させ、一方向のみ解放状態にて、巻回電極体を封入する。続いて、正極リード、及び負極リードと外装部材の間に密着フィルムを挿入する。続いて、解放部から上記調整した電解液を所定量投入し、真空含浸を行う。含浸後、解放部を真空熱融着法により接着させる。以上のようにして、ラミネートフィルム型二次電池３０を製造することができる。   Subsequently, the electrolytic solution is adjusted. Subsequently, the positive electrode lead 32 is attached to the positive electrode current collector and the negative electrode lead 33 is attached to the negative electrode current collector by ultrasonic welding or the like. Subsequently, the positive electrode and the negative electrode are laminated or wound via a separator to produce a wound electrode body 31, and a protective tape is bonded to the outermost periphery. Next, the wound body is molded so as to have a flat shape. Subsequently, after sandwiching the wound electrode body between the folded film-shaped exterior member 35, the insulating portions of the exterior member are bonded to each other by a thermal fusion method, and the wound electrode body is released in only one direction. Enclose. Subsequently, an adhesion film is inserted between the positive electrode lead and the negative electrode lead and the exterior member. Subsequently, a predetermined amount of the adjusted electrolytic solution is introduced from the release portion, and vacuum impregnation is performed. After impregnation, the release part is bonded by a vacuum heat fusion method. The laminated film type secondary battery 30 can be manufactured as described above.

上記作製したラミネートフィルム型二次電池３０等の本発明の非水電解質二次電池において、充放電時の負極利用率が９３％以上９９％以下であることが好ましい。負極利用率を９３％以上の範囲とすれば、初回充電効率が低下せず、電池容量の向上を大きくできる。また、負極利用率を９９％以下の範囲とすれば、Ｌｉが析出してしまうことがなく安全性を確保できる。   In the non-aqueous electrolyte secondary battery of the present invention such as the laminated film type secondary battery 30 produced as described above, the negative electrode utilization rate during charge / discharge is preferably 93% or more and 99% or less. If the negative electrode utilization rate is in the range of 93% or more, the initial charge efficiency does not decrease, and the battery capacity can be greatly improved. Moreover, if the negative electrode utilization rate is in the range of 99% or less, Li is not precipitated and safety can be ensured.

以下、本発明の実施例及び比較例を示して本発明をより具体的に説明するが、本発明はこれら実施例に限定されるものではない。   EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples of the present invention, but the present invention is not limited to these examples.

（実施例１−１）
以下の手順により、図４に示したラミネートフィルム型の二次電池３０を作製した。 (Example 1-1)
The laminate film type secondary battery 30 shown in FIG. 4 was produced by the following procedure.

最初に正極を作製した。正極活物質はリチウムニッケルコバルトアルミニウム複合酸化物（ＬｉＮｉ０．７Ｃｏ０．２５Ａｌ０．０５Ｏ）９５質量部と、正極導電助剤（アセチレンブラック）２．５質量部と、正極結着剤（ポリフッ化ビニリデン、ＰＶＤＦ）２．５質量部とを混合し正極合剤とした。続いて正極合剤を有機溶剤（Ｎ−メチル−２−ピロリドン、ＮＭＰ）に分散させてペースト状のスラリーとした。続いてダイヘッドを有するコーティング装置で正極集電体の両面にスラリーを塗布し、熱風式乾燥装置で乾燥した。この時、正極集電体は厚み１５μｍのものを用いた。最後にロールプレスで圧縮成型を行った。 First, a positive electrode was produced. The positive electrode active material is 95 parts by mass of lithium nickel cobalt aluminum composite oxide (LiNi 0.7 Co 0.25 Al 0.05 O), 2.5 parts by mass of positive electrode conductive additive (acetylene black), and a positive electrode binder. (Polyvinylidene fluoride, PVDF) 2.5 parts by mass were mixed to obtain a positive electrode mixture. Subsequently, the positive electrode mixture was dispersed in an organic solvent (N-methyl-2-pyrrolidone, NMP) to obtain a paste slurry. Subsequently, the slurry was applied to both surfaces of the positive electrode current collector with a coating apparatus having a die head, and dried with a hot air drying apparatus. At this time, a positive electrode current collector having a thickness of 15 μm was used. Finally, compression molding was performed with a roll press.

次に負極を作製した。まず、ケイ素系活物質を以下のように作製した。金属ケイ素と二酸化ケイ素を混合した原料（気化出発材）を反応炉へ設置し、１０Ｐａの真空度の雰囲気中で気化させたものを吸着板上に堆積させ、十分に冷却した後、堆積物を取出しボールミルで粉砕した。粒径を調整した後、熱ＣＶＤを行うことで炭素被膜を被覆した。続いて、炭素被膜を被覆したケイ素化合物に対して４質量％に相当する質量のＬｉＨ粉末をアルゴン雰囲気下で混合し、シェイカーで撹拌した。その後、雰囲気制御炉で、攪拌した粉末を７４０℃の熱処理を行うことで改質を行った。次に、改質後の酸化珪素粒子を脱水エタノールとＡｌイソプロポキシドの混合溶液に投入し、撹拌、濾過、乾燥しエタノールを除去した。これにより、酸化アルミニウム及び水酸化アルミニウムの複合体を含む複合層を形成した。複合層の膜厚は３ｎｍであった。ここでは濾過後の濾過液に残ったアルミニウム量から、膜厚を計算した。   Next, a negative electrode was produced. First, a silicon-based active material was prepared as follows. A raw material (vaporization starting material) mixed with metallic silicon and silicon dioxide is placed in a reactor, and the vaporized material in a vacuum atmosphere of 10 Pa is deposited on an adsorption plate and cooled sufficiently. The take-out ball mill grinded. After adjusting the particle size, the carbon film was coated by performing thermal CVD. Subsequently, LiH powder having a mass corresponding to 4% by mass with respect to the silicon compound coated with the carbon coating was mixed in an argon atmosphere and stirred with a shaker. Thereafter, the agitated powder was modified by heat treatment at 740 ° C. in an atmosphere control furnace. Next, the modified silicon oxide particles were put into a mixed solution of dehydrated ethanol and Al isopropoxide, stirred, filtered and dried to remove ethanol. Thereby, a composite layer containing a composite of aluminum oxide and aluminum hydroxide was formed. The film thickness of the composite layer was 3 nm. Here, the film thickness was calculated from the amount of aluminum remaining in the filtrate after filtration.

以上のようにして作製したケイ素系活物質と、炭素系活物質を１：９の質量比で配合し、負極活物質を作製した。ここで、炭素系活物質としては、ピッチ層で被覆した天然黒鉛及び人造黒鉛を５：５の質量比で混合したものを使用した。また、炭素系活物質のメディアン径は２０μｍであった。   The negative electrode active material was produced by blending the silicon-based active material prepared as described above and the carbon-based active material in a mass ratio of 1: 9. Here, as the carbon-based active material, a mixture of natural graphite and artificial graphite coated with a pitch layer at a mass ratio of 5: 5 was used. The median diameter of the carbon-based active material was 20 μm.

次に、作製した負極活物質、導電助剤１（カーボンナノチューブ、ＣＮＴ）、導電助剤２（メディアン径が約５０ｎｍの炭素微粒子）、スチレンブタジエンゴム（スチレンブタジエンコポリマー、以下、ＳＢＲと称する）、カルボキシメチルセルロース（以下、ＣＭＣと称する）９２．５：１：１：２．５：３の乾燥質量比で混合した後、純水で希釈し負極合剤スラリーとした。尚、上記のＳＢＲ、ＣＭＣは負極バインダー（負極結着剤）である。ここで、負極合剤スラリーの安定性を測定するため、作製した負極合剤スラリーの一部を二次電池の作製用のものとは別に３０ｇ取り出し、２０℃で保存し、負極合剤スラリー作製後から、６時間後、２４時間後、４８時間後、７２時間後、及び１週間後のガス発生状況を確認した。   Next, the produced negative electrode active material, conductive additive 1 (carbon nanotube, CNT), conductive additive 2 (carbon fine particles having a median diameter of about 50 nm), styrene butadiene rubber (styrene butadiene copolymer, hereinafter referred to as SBR), Carboxymethylcellulose (hereinafter referred to as CMC) was mixed at a dry mass ratio of 92.5: 1: 1: 2.5: 3, and then diluted with pure water to obtain a negative electrode mixture slurry. In addition, said SBR and CMC are negative electrode binders (negative electrode binder). Here, in order to measure the stability of the negative electrode mixture slurry, 30 g of a part of the prepared negative electrode mixture slurry is taken out separately from the one for preparing the secondary battery, stored at 20 ° C., and the negative electrode mixture slurry is prepared. Afterward, the gas generation status after 6 hours, 24 hours, 48 hours, 72 hours, and 1 week was confirmed.

また、負極集電体としては、電解銅箔（厚さ１５μｍ）を用いた。最後に、負極合剤スラリーを負極集電体に塗布し真空雰囲気中で１００℃×１時間の乾燥を行った。乾燥後の、負極の片面における単位面積あたりの負極活物質層の堆積量（面積密度とも称する）は５ｍｇ／ｃｍ２であった。 Further, as the negative electrode current collector, an electrolytic copper foil (thickness 15 μm) was used. Finally, the negative electrode mixture slurry was applied to the negative electrode current collector and dried in a vacuum atmosphere at 100 ° C. for 1 hour. The amount of deposition (also referred to as area density) of the negative electrode active material layer per unit area on one side of the negative electrode after drying was 5 mg / cm 2 .

次に、溶媒として、フルオロエチレンカーボネート（ＦＥＣ）、エチレンカーボネート（ＥＣ）及びジエチルカーボネート（ＤＥＣ））を混合したのち、電解質塩（六フッ化リン酸リチウム：ＬｉＰＦ６）を溶解させて電解液を調製した。この場合には、溶媒の組成を体積比でＦＥＣ：ＥＣ：ＤＥＣ＝１：２：７とし、電解質塩の含有量を溶媒に対して１．０ｍｏｌ／ｋｇとした。さらに、得られた電解液にビニレンカーボネート（ＶＣ）を１．５質量％添加した。 Next, after mixing fluoroethylene carbonate (FEC), ethylene carbonate (EC) and diethyl carbonate (DEC) as a solvent, an electrolyte salt (lithium hexafluorophosphate: LiPF 6 ) is dissolved to obtain an electrolyte solution. Prepared. In this case, the composition of the solvent was FEC: EC: DEC = 1: 2: 7 in a volume ratio, and the content of the electrolyte salt was 1.0 mol / kg with respect to the solvent. Furthermore, 1.5% by mass of vinylene carbonate (VC) was added to the obtained electrolytic solution.

次に、以下のようにして二次電池を組み立てた。最初に、正極集電体の一端にアルミリードを超音波溶接し、負極集電体にはニッケルリードを溶接した。続いて、正極、セパレータ、負極、セパレータをこの順に積層し、長手方向に巻回させ巻回電極体を得た。その捲き終わり部分をＰＥＴ保護テープで固定した。セパレータは多孔性ポリプロピレンを主成分とするフィルムにより多孔性ポリエチレンを主成分とするフィルムに挟まれた積層フィルム１２μｍを用いた。続いて、外装部材間に電極体を挟んだのち、一辺を除く外周縁部同士を熱融着し、内部に電極体を収納した。外装部材はナイロンフィルム、アルミ箔及び、ポリプロピレンフィルムが積層されたアルミラミネートフィルムを用いた。続いて、開口部から調整した電解液を注入し、真空雰囲気下で含浸した後、熱融着し封止した。   Next, a secondary battery was assembled as follows. First, an aluminum lead was ultrasonically welded to one end of the positive electrode current collector, and a nickel lead was welded to the negative electrode current collector. Subsequently, a positive electrode, a separator, a negative electrode, and a separator were laminated in this order and wound in the longitudinal direction to obtain a wound electrode body. The end portion was fixed with a PET protective tape. As the separator, a laminated film of 12 μm sandwiched between a film mainly composed of porous polyethylene and a film mainly composed of porous polypropylene was used. Subsequently, after sandwiching the electrode body between the exterior members, the outer peripheral edges except for one side were heat-sealed, and the electrode body was housed inside. As the exterior member, a nylon film, an aluminum foil, and an aluminum laminate film in which a polypropylene film was laminated were used. Subsequently, the prepared electrolyte was injected from the opening, impregnated in a vacuum atmosphere, and then heat-sealed and sealed.

以上のようにして作製した二次電池のサイクル特性及び初回充放電特性を評価した。   The cycle characteristics and initial charge / discharge characteristics of the secondary batteries produced as described above were evaluated.

サイクル特性については、以下のようにして調べた。最初に、電池安定化のため２５℃の雰囲気下、０．２Ｃで２サイクル充放電を行い、２サイクル目の放電容量を測定した。続いて、総サイクル数が４９９サイクルとなるまで充放電を行い、その都度放電容量を測定した。最後に、０．２Ｃ充放電で得られた５００サイクル目の放電容量を２サイクル目の放電容量で割り、容量維持率（以下、単に維持率ともいう）を算出した。通常サイクル、すなわち３サイクル目から４９９サイクル目までは、充電０．７Ｃ、放電０．５Ｃで充放電を行った。   The cycle characteristics were examined as follows. First, in order to stabilize the battery, charge and discharge was performed for 2 cycles at 0.2 C in an atmosphere at 25 ° C., and the discharge capacity at the second cycle was measured. Subsequently, charge and discharge were performed until the total number of cycles reached 499 cycles, and the discharge capacity was measured each time. Finally, the discharge capacity at the 500th cycle obtained by 0.2 C charge / discharge was divided by the discharge capacity at the second cycle to calculate a capacity retention rate (hereinafter also simply referred to as a retention rate). In the normal cycle, that is, from the 3rd cycle to the 499th cycle, charging and discharging were performed with a charge of 0.7 C and a discharge of 0.5 C.

初回充放電特性を調べる場合には、初回効率（以下では初期効率と呼ぶ場合もある）を算出した。初回効率は、初回効率（％）＝（初回放電容量／初回充電容量）×１００で表される式から算出した。雰囲気温度は、サイクル特性を調べた場合と同様にした。   When examining the initial charge / discharge characteristics, the initial efficiency (hereinafter sometimes referred to as initial efficiency) was calculated. The initial efficiency was calculated from an equation represented by initial efficiency (%) = (initial discharge capacity / initial charge capacity) × 100. The ambient temperature was the same as when the cycle characteristics were examined.

（実施例１−２〜実施例１−４）
複合層における金属酸化物種及び金属水酸化物種を表１に示すような元素を含むものに変更したこと以外、実施例１−１と同様に、二次電池の製造を行った。金属酸化物種及び金属水酸化物種の変更は、複合層形成時のゾルゲル反応に使用する金属アルコキシドの種類を変更することで可能である。 (Example 1-2 to Example 1-4)
A secondary battery was manufactured in the same manner as in Example 1-1 except that the metal oxide species and metal hydroxide species in the composite layer were changed to those containing elements as shown in Table 1. The metal oxide species and the metal hydroxide species can be changed by changing the type of metal alkoxide used for the sol-gel reaction when forming the composite layer.

（比較例１−１）
ケイ素化合物の作製後に、炭素被膜の形成、ケイ素化合物の改質、及び複合層の形成のいずれの工程も行わなかった以外、実施例１−１と同様に、二次電池の製造を行った。 (Comparative Example 1-1)
A secondary battery was manufactured in the same manner as in Example 1-1, except that after the production of the silicon compound, none of the steps of forming the carbon coating, modifying the silicon compound, and forming the composite layer was performed.

（比較例１−２）
ケイ素化合物の作製後に、炭素被膜の形成を行ったが、ケイ素化合物の改質、及び複合層の形成は行わなかったこと以外、実施例１−１と同様に、二次電池の製造を行った。 (Comparative Example 1-2)
After the formation of the silicon compound, the carbon film was formed, but the secondary battery was manufactured in the same manner as in Example 1-1 except that the silicon compound was not modified and the composite layer was not formed. .

（比較例１−３）
ケイ素化合物の作製後に、炭素被膜の形成、及びケイ素化合物の改質を行ったが、複合層の形成は行わなかったこと以外、実施例１−１と同様に、二次電池の製造を行った。 (Comparative Example 1-3)
After the formation of the silicon compound, the secondary battery was manufactured in the same manner as in Example 1-1 except that the carbon film was formed and the silicon compound was modified, but the composite layer was not formed. .

上記実施例及び比較例におけるケイ素化合物の物性は以下のとおりである。上記の全ての実施例及び比較例においてＳｉＯｘで表されるケイ素化合物のｘの値が１．０であり、ケイ素化合物のメディアン径Ｄ５０は４μｍであった。また、比較例１−１及び比較例１−２のような、未改質のケイ素化合物のＸ線回折により得られるＳｉ（１１１）結晶面に起因する回折ピークの半値幅（２θ）は２．５９３°であり、その結晶面Ｓｉ（１１１）に起因する結晶子サイズは３．２９ｎｍであった。また、これらの比較例１−１、１−２以外における、改質後のケイ素化合物のＸ線回折により得られるＳｉ（１１１）結晶面に起因する回折ピークの半値幅（２θ）は２．２５７°であり、その結晶面Ｓｉ（１１１）に起因する結晶子サイズは３．７７ｎｍであった。これは、改質に熱ドープ法を用いたため、ケイ素化合物の一部が不均化し、結晶化が進んだためである。改質後のケイ素化合物はＬｉ２ＳｉＯ３を含んでいた。 The physical properties of the silicon compounds in the above Examples and Comparative Examples are as follows. In all the examples and comparative examples described above, the value x of the silicon compound represented by SiO x was 1.0, and the median diameter D 50 of the silicon compound was 4 μm. Moreover, the half width (2θ) of the diffraction peak caused by the Si (111) crystal plane obtained by X-ray diffraction of the unmodified silicon compound as in Comparative Example 1-1 and Comparative Example 1-2 is 2. The crystallite size attributable to the crystal plane Si (111) was 3.29 nm. In addition to these Comparative Examples 1-1 and 1-2, the half-value width (2θ) of the diffraction peak due to the Si (111) crystal plane obtained by X-ray diffraction of the modified silicon compound is 2.257. The crystallite size attributable to the crystal plane Si (111) was 3.77 nm. This is because part of the silicon compound was disproportionated and crystallization progressed because the thermal doping method was used for the modification. The silicon compound after modification contained Li 2 SiO 3 .

また、実施例１−１〜１−４、比較例１−２、１−３において、炭素被膜の被覆量が、ケイ素化合物と炭素被膜の合計に対し、５質量％であった。また、上記の全ての実施例及び比較例において、２９Ｓｉ−ＭＡＳ−ＮＭＲ スペクトルから得られるケミカルシフト値として−９５〜−１５０ｐｐｍに与えられるＳｉＯ２領域に由来するピークが発現した。また、比較例１−１、比較例１−２では、２９Ｓｉ−ＭＡＳ−ＮＭＲ スペクトルから得られるケミカルシフト値として−７５ｐｐｍ付近に与えられるＬｉ２ＳｉＯ３に由来するピークの強度Ａと上記ＳｉＯ２領域に由来するピークの強度Ｂとの関係がＡ＜Ｂであった。その他の実施例、比較例では、上記関係はＡ＞Ｂであった。実施例１−１において得られた２９Ｓｉ−ＭＡＳ−ＮＭＲスペクトルを図５に示す。 Moreover, in Examples 1-1 to 1-4 and Comparative Examples 1-2 and 1-3, the coating amount of the carbon coating was 5% by mass with respect to the total of the silicon compound and the carbon coating. Moreover, in all the Examples and Comparative Examples described above, a peak derived from the SiO 2 region given to −95 to −150 ppm as a chemical shift value obtained from the 29 Si-MAS-NMR spectrum appeared. In Comparative Example 1-1 and Comparative Example 1-2, the peak intensity A derived from Li 2 SiO 3 given in the vicinity of −75 ppm as the chemical shift value obtained from the 29 Si-MAS-NMR spectrum and the above SiO 2 The relationship with the intensity B of the peak derived from the region was A <B. In other examples and comparative examples, the above relationship was A> B. The 29 Si-MAS-NMR spectrum obtained in Example 1-1 is shown in FIG.

また、上記のように作製した負極と対極リチウムとから、２０３２サイズのコイン電池型の試験セルを作製し、その放電挙動を評価した。より具体的には、まず、対極Ｌｉで０Ｖまで定電流定電圧充電を行い、電流密度が０．０５ｍＡ／ｃｍ２に達した時点で充電を終止させた。その後、１．２Ｖまで定電流放電を行った。この時の電流密度は０．２ｍＡ／ｃｍ２であった。このような充放電により得られたデータから、縦軸を容量の変化率（ｄＱ／ｄＶ）、横軸を電圧（Ｖ）としてグラフを描き、Ｖが０．４〜０．５５（Ｖ）の範囲にピークが得られるかを確認した。その結果、比較例１−１、１−２以外の全ての実施例、比較例にてピークが確認された。 Further, a 2032 size coin cell type test cell was prepared from the negative electrode and the counter electrode lithium prepared as described above, and the discharge behavior was evaluated. More specifically, first, constant current and constant voltage charging was performed up to 0 V with the counter electrode Li, and the charging was terminated when the current density reached 0.05 mA / cm 2 . Then, constant current discharge was performed to 1.2V. The current density at this time was 0.2 mA / cm 2 . From the data obtained by such charging and discharging, a graph is drawn with the vertical axis representing the rate of change in capacity (dQ / dV) and the horizontal axis representing the voltage (V), where V is 0.4 to 0.55 (V). It was confirmed whether a peak was obtained in the range. As a result, peaks were confirmed in all Examples and Comparative Examples other than Comparative Examples 1-1 and 1-2.

実施例１−１〜１−４、比較例１−１、１−２、１−３の評価結果を表１に示す。   Table 1 shows the evaluation results of Examples 1-1 to 1-4 and Comparative Examples 1-1, 1-2, and 1-3.

Figure 2017010645
Figure 2017010645

表１の実施例１−１〜実施例１−４のように、本発明の負極活物質を使用した二次電池では、Ｌｉを用いた改質による、サイクル特性や初回効率といった電池特性の向上効果を得られるうえに、ガス発生を大幅に抑制することができた。特に、実施例１−１では、スラリー作製から１週間経過後にしかガスの発生が確認されなかった。   As in Example 1-1 to Example 1-4 in Table 1, in the secondary battery using the negative electrode active material of the present invention, battery characteristics such as cycle characteristics and initial efficiency are improved by reforming using Li. In addition to obtaining the effect, the generation of gas could be greatly suppressed. In particular, in Example 1-1, the generation of gas was confirmed only after a lapse of one week from the preparation of the slurry.

一方、改質したケイ素系活物質粒子に複合層を形成しなかった比較例１−３では、スラリー作成から６時間経過時点でガスが発生していた。上記のように、スラリー作製直後から作製後６時間経過前の間でガス発生の有無を確認していないため、比較例１−３ではスラリー作製後から６時間以内にガスが発生してしまったと言える。ガス発生後のスラリーは銅箔（集電体）との剥離強度が低下するため、取扱いが難しい。工業的に電極を作製する場合には、スラリーのポットライフは最低でも６時間は必要であるため、比較例１−３の負極活物質は工業的な生産に使用するに耐えないものであるといえる。また、改質を行っていない比較例１−１、１−２ではガスの発生は無かったものの、実施例に比べて電池特性が劣る。比較例１−２では、ケイ素系活物質粒子が炭素被膜を有しているため、比較例１−１よりも電池特性は良好であるが、十分な値とは言えない。   On the other hand, in Comparative Example 1-3 in which the composite layer was not formed on the modified silicon-based active material particles, gas was generated when 6 hours had elapsed since the slurry was created. As described above, since the presence or absence of gas generation was not confirmed between immediately after slurry preparation and 6 hours after preparation, in Comparative Example 1-3, gas was generated within 6 hours after slurry preparation. I can say that. The slurry after gas generation is difficult to handle because the peel strength from the copper foil (current collector) decreases. When an electrode is produced industrially, since the pot life of the slurry requires at least 6 hours, the negative electrode active material of Comparative Example 1-3 cannot be used for industrial production. I can say that. Further, in Comparative Examples 1-1 and 1-2 in which no reforming was performed, no gas was generated, but the battery characteristics were inferior to those of the Examples. In Comparative Example 1-2, since the silicon-based active material particles have a carbon coating, the battery characteristics are better than Comparative Example 1-1, but it cannot be said to be a sufficient value.

（実施例２−１、２−２、比較例２−１、２−２）
ケイ素化合物のバルク内酸素量を調整したことを除き、実施例１−１と同様に、二次電池の製造を行った。この場合、気化出発材の比率や温度を変化させることで、酸素量を調整した。実施例２−１、２−２、比較例２−１、２−２における、ＳｉＯｘで表されるケイ素化合物のｘの値を表２中に示した。 (Examples 2-1 and 2-2, Comparative Examples 2-1 and 2-2)
A secondary battery was manufactured in the same manner as Example 1-1 except that the amount of oxygen in the bulk of the silicon compound was adjusted. In this case, the amount of oxygen was adjusted by changing the ratio and temperature of the vaporized starting material. The values of x of the silicon compounds represented by SiO x in Examples 2-1 and 2-2 and Comparative Examples 2-1 and 2-2 are shown in Table 2.

Figure 2017010645
Figure 2017010645

ケイ素化合物中の酸素量が減る、すなわちｘ＜０．５となると、Ｓｉリッチとなり、サイクル維持率が大幅に低下した。また酸素リッチの場合、すなわちｘ＞１．６となる場合、ケイ素酸化物の抵抗が高くなり、サイクル維持率が大幅に低下した。   When the amount of oxygen in the silicon compound was reduced, that is, when x <0.5, Si was rich, and the cycle retention rate was significantly reduced. Further, in the case of oxygen rich, that is, when x> 1.6, the resistance of the silicon oxide was increased, and the cycle maintenance ratio was greatly reduced.

（実施例３−１〜３−６）
複合層の膜厚を表３に示すように変更したこと以外、実施例１−１と同様に、二次電池の製造を行った。膜厚は、脱水エタノールと改質後のケイ素化合物に対するＡｌイソプロポキシドの質量比を変化させることで調整した。なお、膜厚はＴＥＭでも測定可能であるが、ここでは濾過後の濾過液に残ったアルミニウム量から、膜厚を計算した。また、実施例３−３における膜厚（３ｎｍ）に関しては、ＴＥＭで画像を確認し、上記計算法で得た膜厚の算出値がＴＥＭで測定する膜厚値とほぼ一致することを確認した。 (Examples 3-1 to 3-6)
A secondary battery was manufactured in the same manner as in Example 1-1 except that the thickness of the composite layer was changed as shown in Table 3. The film thickness was adjusted by changing the mass ratio of Al isopropoxide to dehydrated ethanol and the modified silicon compound. The film thickness can also be measured by TEM, but here the film thickness was calculated from the amount of aluminum remaining in the filtrate after filtration. Moreover, about the film thickness (3 nm) in Example 3-3, the image was confirmed with TEM and it was confirmed that the calculated value of the film thickness obtained by the said calculation method substantially corresponds with the film thickness value measured by TEM. .

Figure 2017010645
Figure 2017010645

表３から分かるように、複合層の厚さが１０ｎｍ以下で、十分なガス発生の抑制効果に加え、電池特性の向上効果を、より十分に得られることが分かった。また、複合層の厚さが５ｎｍ以下、特には２〜３ｎｍで特に良好な電池特性の向上効果が得られることが分かった。   As can be seen from Table 3, it was found that when the thickness of the composite layer is 10 nm or less, the effect of improving battery characteristics can be obtained more sufficiently in addition to the sufficient effect of suppressing gas generation. In addition, it was found that particularly good battery characteristic improvement effects can be obtained when the thickness of the composite layer is 5 nm or less, particularly 2 to 3 nm.

（実施例４−１〜実施例４−５）
複合層の膜厚を表４に示すように変更したことと、改質方法を電気化学的手法としたこと以外、実施例１−１と同様に、二次電池の製造を行った。より具体的には、改質は、図３に示した装置内で、エチレンカーボネート及びジメチルカーボネートの体積比が３：７の混合溶媒（電解質塩を１．３ｍｏｌ／ｋｇの濃度で含んでいる。）中で電気化学法を用いバルク改質を行った。 (Example 4-1 to Example 4-5)
A secondary battery was manufactured in the same manner as in Example 1-1 except that the film thickness of the composite layer was changed as shown in Table 4 and the modification method was an electrochemical method. More specifically, the reforming includes a mixed solvent having a volume ratio of ethylene carbonate and dimethyl carbonate of 3: 7 (electrolyte salt at a concentration of 1.3 mol / kg) in the apparatus shown in FIG. ) Was subjected to bulk modification using an electrochemical method.

Figure 2017010645
Figure 2017010645

改質方法を電気化学的手法とした場合であっても、表４に示すように、複合層の厚さが１０ｎｍ以下で、ガス発生の抑制効果に加え、電池特性の向上効果がより十分に得られることが分かった。また、この場合にも、複合層の厚さが５ｎｍ以下、特には２〜３ｎｍで特に良好な電池特性の向上効果が得られることが分かった。   Even when the reforming method is an electrochemical method, as shown in Table 4, the composite layer thickness is 10 nm or less, and in addition to the effect of suppressing gas generation, the effect of improving battery characteristics is more sufficiently achieved. It turns out that it is obtained. Also in this case, it was found that particularly good battery characteristic improvement effect can be obtained when the thickness of the composite layer is 5 nm or less, particularly 2 to 3 nm.

（実施例５−１、５−２）
ケイ素化合物を２９Ｓｉ−ＭＡＳ−ＮＭＲ スペクトルから得られるケミカルシフト値として−９５〜−１５０ｐｐｍに与えられるＳｉＯ２領域に由来するピークを持たないものとしたこと以外、実施例１−１と同様に二次電池を作製した。改質時にＬｉ量を増加させることで、ＳｉＯ２領域に由来するピークの強度を大幅に低減した。そして、その後、水系スラリーに耐えられる程度にまでケイ素化合物からＬｉを脱離することで、ＮＭＲで確認可能なＳｉＯ２領域が無いケイ素系活物質を作製した。 (Examples 5-1 and 5-2)
Except that the silicon compound does not have a peak derived from the SiO 2 region given to -95 to -150 ppm as the chemical shift value obtained from the 29 Si-MAS-NMR spectrum, the same as in Example 1-1. A secondary battery was produced. By increasing the amount of Li during the modification, the intensity of the peak derived from the SiO 2 region was greatly reduced. Thereafter, Li was desorbed from the silicon compound to the extent that it can withstand the aqueous slurry, thereby producing a silicon-based active material having no SiO 2 region that can be confirmed by NMR.

また、実施例５−２では、改質手法を電気化学的手法に変更した。   In Example 5-2, the modification method was changed to an electrochemical method.

Figure 2017010645
Figure 2017010645

実施例５−１、５−２では、それぞれ、２４時間後と４８時間後にガスの発生が確認された。一方で、ＮＭＲによって測定されるＳｉＯ２領域に由来するピークの有無以外、実施例５−１と同条件でスラリーを作製した実施例１−１や、実施例５−２と上記ピークの有無以外同条件でスラリーを作製した実施例３−３では、上述のように、ガスの発生は１週間後に確認された。このことから、ケイ素系活物質にＮＭＲで確認可能なＳｉＯ２領域が含まれている方が、ガスの発生を抑制する効果がより高いことが分かった。また、実施例５−１、５−２のように、Ｌｉ化合物が多く、スラリーに対する安定性が比較的低くなり得る場合であっても、本発明のように複合層を形成すれば、ガス発生時間を２４時間以上とでき、従来に比べ大幅にガスの発生を抑制できていることも確認できた。 In Examples 5-1 and 5-2, generation of gas was confirmed after 24 hours and 48 hours, respectively. On the other hand, except for the presence or absence of a peak derived from the SiO 2 region measured by NMR, Example 1-1 and Example 5-2 other than the presence or absence of the peak described above were prepared under the same conditions as Example 5-1. In Example 3-3 in which the slurry was produced under the same conditions, as described above, gas generation was confirmed after one week. From this, it was found that the effect of suppressing the generation of gas is higher when the silicon-based active material contains a SiO 2 region that can be confirmed by NMR. In addition, even if the Li compound is large and the stability to the slurry can be relatively low as in Examples 5-1 and 5-2, if the composite layer is formed as in the present invention, gas generation is caused. The time was 24 hours or more, and it was also confirmed that the generation of gas could be greatly suppressed compared to the conventional case.

（実施例６−１）
ケイ素化合物をＬｉ２ＳｉＯ３に由来するピークの強度Ａと上記ＳｉＯ２領域に由来するピークの強度Ｂとの関係がＡ＜Ｂのものとしたこと以外、実施例１−１と同様に二次電池を作製した。この場合、改質時にＬｉ量を減らすことで、Ｌｉ２ＳｉＯ３の量を減らし、Ｌｉ２ＳｉＯ３に由来するピークの強度Ａを小さくした。 (Example 6-1)
The silicon compound was secondary as in Example 1-1 except that the relationship between the peak intensity A derived from Li 2 SiO 3 and the peak intensity B derived from the SiO 2 region was A <B. A battery was produced. In this case, the amount of Li 2 SiO 3 was reduced by reducing the amount of Li during the modification, and the peak intensity A derived from Li 2 SiO 3 was reduced.

Figure 2017010645
Figure 2017010645

ケイ素化合物に、ＮＭＲで確認できる二酸化ケイ素領域を強く残した場合、ガス発生にマイルドな方向（ガス発生を抑制する方向）となる。ここでは、測定の方法上、ガス発生までの時間が、ピーク強度の関係Ａ＞Ｂを満たす実施例１−１と同じ１週間と評価されたが、実際には、実施例６−１のガス発生までの時間は、実施例１−１のガス発生までの時間より長いと考えられる。しかしながら、実施例６−１では、実施例１−１に比べ若干初期効率が低下した。   When a silicon dioxide region that can be confirmed by NMR is strongly left in the silicon compound, the direction is mild to gas generation (a direction in which gas generation is suppressed). Here, in the measurement method, the time until gas generation was evaluated as the same one week as Example 1-1 satisfying the relationship A> B of the peak intensity, but actually the gas of Example 6-1 was evaluated. It is considered that the time until generation is longer than the time until gas generation in Example 1-1. However, the initial efficiency in Example 6-1 was slightly lower than that in Example 1-1.

（実施例７−１）
ケイ素系活物質をＶ−ｄＱ／ｄＶ曲線において、Ｖが０．４０Ｖ〜０．５５Ｖの範囲にピークが得られないものとしたこと以外、実施例１−１と同様に二次電池を作製した。 (Example 7-1)
A secondary battery was fabricated in the same manner as in Example 1-1 except that the silicon-based active material had no V peak in the range of 0.40 V to 0.55 V in the V-dQ / dV curve. .

Figure 2017010645
Figure 2017010645

放電カーブ形状がより鋭く立ち上がるためには、ケイ素化合物（ＳｉＯｘ）において、ケイ素（Ｓｉ）と同様の放電挙動を示す必要がある。上記の範囲にピークが存在しない場合、ケイ素化合物は比較的緩やかな放電カーブとなるため、組みセルにした場合、若干初期効率が低下する結果となった。   In order for the discharge curve shape to rise more sharply, the silicon compound (SiOx) needs to exhibit a discharge behavior similar to that of silicon (Si). When there is no peak in the above range, the silicon compound has a relatively gentle discharge curve. Therefore, when the assembled cell is used, the initial efficiency slightly decreases.

（実施例８−１〜８−９）
ケイ素化合物の結晶性を変化させた他は、実施例１−１と同様に二次電池の製造を行った。ケイ素化合物の結晶性の変化は、ケイ素化合物の作製後に非大気雰囲気下で熱処理することで制御可能である。なお、熱ドープ法による改質では、ケイ素化合物に一定以上の熱がかかる。そこで、実施例８−８、８−９では、より非晶質に近い材料において、低結晶性を維持するために電気化学法で改質を行っている。 (Examples 8-1 to 8-9)
A secondary battery was manufactured in the same manner as in Example 1-1 except that the crystallinity of the silicon compound was changed. The change in crystallinity of the silicon compound can be controlled by heat treatment in a non-air atmosphere after the silicon compound is produced. In the modification by the thermal doping method, a certain amount of heat is applied to the silicon compound. Therefore, in Examples 8-8 and 8-9, the material close to amorphous is modified by an electrochemical method in order to maintain low crystallinity.

Figure 2017010645
Figure 2017010645

特に半値幅（２θ）が１．２°以上で、尚且つＳｉ（１１１）面に起因する結晶子サイズが７．５ｎｍ以下の低結晶性材料で高い維持率が得られた。   In particular, a high retention rate was obtained with a low crystalline material having a half width (2θ) of 1.2 ° or more and a crystallite size attributable to the Si (111) plane of 7.5 nm or less.

（実施例９−１〜実施例９−６）
ケイ素化合物のメディアン径を表９のように変化させたこと以外、実施例１−１と同様に二次電池の製造を行った。 (Example 9-1 to Example 9-6)
A secondary battery was manufactured in the same manner as in Example 1-1 except that the median diameter of the silicon compound was changed as shown in Table 9.

Figure 2017010645
Figure 2017010645

ケイ素化合物のメディアン径が０．５μｍ以上であれば、維持率が向上した。これは、ケイ素化合物の表面積が大すぎず、副反応が起きる面積を小さくできたためと考えられる。一方、メディアン径が１５μｍ以下であれば、充電時に粒子が割れ難く、充放電時に新生面によるＳＥＩ（固体電解質界面）が生成し難いため、可逆Ｌｉの損失を抑制することができる。   When the median diameter of the silicon compound was 0.5 μm or more, the maintenance ratio was improved. This is presumably because the surface area of the silicon compound was not too large and the area where the side reaction occurred could be reduced. On the other hand, if the median diameter is 15 μm or less, the particles are difficult to break during charging, and SEI (solid electrolyte interface) due to the new surface is difficult to be generated during charging and discharging, so that loss of reversible Li can be suppressed.

なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。   The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

１…ケイ素化合物、 ２…炭素被膜、 ３…複合層、
３ａ…アルミニウム酸化物領域、 ３ｂ…アルミニウム水酸化物領域、
１０…負極、 １１…負極集電体、 １２…負極活物質層、
２０…Ｌｉドープ改質装置、 ２１…陽電極（リチウム源、改質源）、
２２…酸化ケイ素の粉末、 ２３…有機溶媒、 ２４…セパレータ、
２５…粉末格納容器、 ２６…電源、 ２７…浴槽、
３０…リチウムイオン二次電池（ラミネートフィルム型）、 ３１…電極体、
３２…正極リード（正極アルミリード）、
３３…負極リード（負極ニッケルリード）、 ３４…密着フィルム、
３５…外装部材。 1 ... silicon compound, 2 ... carbon coating, 3 ... composite layer,
3a ... aluminum oxide region, 3b ... aluminum hydroxide region,
10 ... negative electrode, 11 ... negative electrode current collector, 12 ... negative electrode active material layer,
20 ... Li doping reformer, 21 ... Positive electrode (lithium source, reforming source),
22 ... Silicon oxide powder, 23 ... Organic solvent, 24 ... Separator,
25 ... Powder storage container, 26 ... Power supply, 27 ... Bathtub,
30 ... Lithium ion secondary battery (laminate film type), 31 ... Electrode body,
32 ... Positive electrode lead (positive electrode aluminum lead),
33 ... negative electrode lead (negative electrode nickel lead), 34 ... adhesion film,
35 ... exterior member.

Claims (13)

負極活物質粒子を有し、該負極活物質粒子はＬｉ化合物が含まれるケイ素化合物（ＳｉＯｘ：０．５≦ｘ≦１．６）を含有するものである非水電解質二次電池用負極活物質であって、
前記ケイ素化合物の表面の少なくとも一部が炭素被膜で被覆されたものであり、
前記ケイ素化合物の表面若しくは前記炭素被膜の表面、又はこれらの両方の少なくとも一部が、非晶質の金属酸化物及び金属水酸化物から成る複合体を含む複合層で被覆されたものであることを特徴とする非水電解質二次電池用負極活物質。 Negative electrode active material particles for non-aqueous electrolyte secondary batteries having negative electrode active material particles, wherein the negative electrode active material particles contain a silicon compound containing a Li compound (SiO x : 0.5 ≦ x ≦ 1.6) A substance,
At least a part of the surface of the silicon compound is coated with a carbon film,
At least a part of the surface of the silicon compound or the surface of the carbon coating, or both of them is coated with a composite layer containing a composite made of an amorphous metal oxide and metal hydroxide. A negative electrode active material for a non-aqueous electrolyte secondary battery. 前記金属酸化物及び金属水酸化物は、アルミニウム、マグネシウム、チタニウム、及びジルコニウムのうち少なくとも１種の元素を含むことを特徴とする請求項１に記載の非水電解質二次電池用負極活物質。   2. The negative electrode active material for a non-aqueous electrolyte secondary battery according to claim 1, wherein the metal oxide and the metal hydroxide contain at least one element selected from aluminum, magnesium, titanium, and zirconium. 前記複合層の厚さが１０ｎｍ以下であることを特徴とする請求項１又は請求項２に記載の非水電解質二次電池用負極活物質。   The negative electrode active material for a nonaqueous electrolyte secondary battery according to claim 1 or 2, wherein the composite layer has a thickness of 10 nm or less. 前記複合層の厚さが５ｎｍ以下であることを特徴とする請求項１から請求項３のいずれか１項に記載の非水電解質二次電池用負極活物質。   The negative electrode active material for a nonaqueous electrolyte secondary battery according to any one of claims 1 to 3, wherein the composite layer has a thickness of 5 nm or less. 前記ケイ素化合物は、前記Ｌｉ化合物としてＬｉ２ＳｉＯ３を含むことを特徴とする請求項１から請求項４のいずれか１項に記載の非水電解質二次電池用負極活物質。 Said silicon compound, a negative electrode active material for a non-aqueous electrolyte secondary battery as claimed in any one of claims 4, characterized in that it comprises a Li 2 SiO 3 as the Li compound. 前記ケイ素化合物が、２９Ｓｉ−ＭＡＳ−ＮＭＲ スペクトルから得られるケミカルシフト値として−９５〜−１５０ｐｐｍに与えられるＳｉＯ２領域に由来するピークを持つことを特徴とする請求項１から請求項５のいずれか１項に記載の非水電解質二次電池負極活物質。 6. The silicon compound according to claim 1, wherein the silicon compound has a peak derived from a SiO 2 region given as −95 to −150 ppm as a chemical shift value obtained from a 29 Si-MAS-NMR spectrum. The non-aqueous electrolyte secondary battery negative electrode active material according to claim 1. 前記ケイ素化合物が、２９Ｓｉ−ＭＡＳ−ＮＭＲ スペクトルから得られるケミカルシフト値として−７５ｐｐｍ付近に与えられるＬｉ２ＳｉＯ３に由来するピークの強度Ａと、−９５〜−１５０ｐｐｍに与えられるＳｉＯ２領域に由来するピークの強度Ｂとが、Ａ＞Ｂの関係を満たすことを特徴とする請求項１から請求項６のいずれか１項に記載の非水電解質二次電池負極活物質。 The silicon compound has a peak intensity A derived from Li 2 SiO 3 given in the vicinity of −75 ppm as a chemical shift value obtained from a 29 Si-MAS-NMR spectrum, and a SiO 2 region given to −95 to −150 ppm. The non-aqueous electrolyte secondary battery negative electrode active material according to any one of claims 1 to 6, wherein the derived peak intensity B satisfies a relationship of A> B. 前記非水電解質二次電池用負極活物質と炭素系活物質とを混合した負極活物質を使用して作製した負極電極と対極リチウムとから成る試験セルを充放電し、放電容量Ｑを前記対極リチウムを基準とする前記負極電極の電位Ｖで微分した微分値ｄＱ／ｄＶと前記電位Ｖとの関係を示すグラフを描いた場合に、前記非水電解質二次電池用負極活物質がリチウムを脱離するよう電流を流す放電時における、前記負極電極の電位Ｖが０．４０Ｖ〜０．５５Ｖの範囲にピークを有するものであることを特徴とする請求項１から請求項７のいずれか１項に記載の非水電解質二次電池用負極活物質。   A test cell composed of a negative electrode prepared by using a negative electrode active material obtained by mixing the negative electrode active material for a nonaqueous electrolyte secondary battery and a carbon-based active material and a counter electrode lithium is charged and discharged, and a discharge capacity Q is set to the counter electrode. When a graph showing the relationship between the differential value dQ / dV differentiated by the potential V of the negative electrode with respect to lithium and the potential V is drawn, the negative electrode active material for the non-aqueous electrolyte secondary battery desorbs lithium. 8. The electric potential V of the negative electrode has a peak in a range of 0.40 V to 0.55 V at the time of discharging in which a current flows so as to be separated. 8. The negative electrode active material for nonaqueous electrolyte secondary batteries as described in 2. 前記ケイ素化合物が、Ｘ線回折により得られるＳｉ（１１１）結晶面に起因する回折ピークの半値幅（２θ）が１．２°以上であると共に、その結晶面に起因する結晶子サイズが７．５ｎｍ以下のものであることを特徴とする請求項１から請求項８のいずれか１項に記載の非水電解質二次電池用負極活物質。   The silicon compound has a half-width (2θ) of a diffraction peak due to the Si (111) crystal plane obtained by X-ray diffraction of 1.2 ° or more and a crystallite size due to the crystal plane of 7. The negative electrode active material for a nonaqueous electrolyte secondary battery according to any one of claims 1 to 8, wherein the negative electrode active material is 5 nm or less. 前記ケイ素化合物のメディアン径が０．５μｍ以上１５μｍ以下のものであることを特徴とする請求項１から請求項９のいずれか１項に記載の非水電解質二次電池用負極活物質。   10. The negative electrode active material for a non-aqueous electrolyte secondary battery according to claim 1, wherein the silicon compound has a median diameter of 0.5 μm or more and 15 μm or less. 11. 請求項１から請求項１０のいずれか１項に記載の非水電解質二次電池用負極活物質を含むことを特徴とする非水電解質二次電池。   The nonaqueous electrolyte secondary battery characterized by including the negative electrode active material for nonaqueous electrolyte secondary batteries of any one of Claims 1-10. 負極活物質粒子を含む非水電解質二次電池用負極材の製造方法であって、
一般式ＳｉＯｘ（０．５≦ｘ≦１．６）で表される酸化珪素粒子を作製する工程と、
前記酸化珪素粒子の表面に炭素被膜を形成する工程と、
前記炭素被膜が被覆された酸化珪素粒子に、Ｌｉを挿入、脱離することで、前記酸化珪素粒子を改質する工程と、
前記改質後の酸化珪素粒子の表面に、非晶質の金属酸化物及び金属水酸化物から成る複合体を含む複合層を形成する工程とを有し、前記複合層を形成された酸化珪素粒子を用いて、非水電解質二次電池用負極材を製造することを特徴とする非水電解質二次電池用負極材の製造方法。 A method for producing a negative electrode material for a non-aqueous electrolyte secondary battery comprising negative electrode active material particles,
Producing silicon oxide particles represented by the general formula SiO x (0.5 ≦ x ≦ 1.6);
Forming a carbon film on the surface of the silicon oxide particles;
Modifying the silicon oxide particles by inserting and desorbing Li to the silicon oxide particles coated with the carbon coating; and
Forming a composite layer containing a composite of an amorphous metal oxide and a metal hydroxide on the surface of the modified silicon oxide particles, and the silicon oxide having the composite layer formed thereon The manufacturing method of the negative electrode material for nonaqueous electrolyte secondary batteries characterized by manufacturing the negative electrode material for nonaqueous electrolyte secondary batteries using particle | grains. 前記複合層形成工程において、金属アルコキシドの加水分解及び脱水縮合によって前記改質後の酸化珪素粒子の表面に前記複合層を形成することを特徴とする請求項１２に記載の非水電解質二次電池用負極材の製造方法。   The non-aqueous electrolyte secondary battery according to claim 12, wherein, in the composite layer forming step, the composite layer is formed on the surface of the modified silicon oxide particles by hydrolysis and dehydration condensation of a metal alkoxide. Manufacturing method for negative electrode material.
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